CN1723083A - Mixed oxide catalyst of rb, ce, cr, ni, fe, bi and mo for the manufacture of acrylonitrile - Google Patents
Mixed oxide catalyst of rb, ce, cr, ni, fe, bi and mo for the manufacture of acrylonitrile Download PDFInfo
- Publication number
- CN1723083A CN1723083A CNA2003801048830A CN200380104883A CN1723083A CN 1723083 A CN1723083 A CN 1723083A CN A2003801048830 A CNA2003801048830 A CN A2003801048830A CN 200380104883 A CN200380104883 A CN 200380104883A CN 1723083 A CN1723083 A CN 1723083A
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- China
- Prior art keywords
- carbon monoxide
- catalyst
- olefin polymeric
- described carbon
- mixture
- 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.)
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- 239000003054 catalyst Substances 0.000 title claims abstract description 122
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 98
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000011777 magnesium Substances 0.000 claims abstract description 62
- 239000011651 chromium Substances 0.000 claims abstract description 59
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 58
- 239000000203 mixture Substances 0.000 claims abstract description 44
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 23
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 22
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 21
- 239000011734 sodium Substances 0.000 claims abstract description 21
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 20
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 20
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 18
- 239000011733 molybdenum Substances 0.000 claims abstract description 18
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 18
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 18
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 18
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 18
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 15
- 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 claims abstract description 15
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims abstract description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052716 thallium Inorganic materials 0.000 claims abstract description 14
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 13
- 229910052796 boron Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 12
- 239000011575 calcium Substances 0.000 claims abstract description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 11
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- 239000011591 potassium Substances 0.000 claims abstract description 11
- 150000001336 alkenes Chemical class 0.000 claims abstract description 10
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 7
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 7
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 7
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 229910052799 carbon Inorganic materials 0.000 claims description 32
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 26
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 229910021529 ammonia Inorganic materials 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001882 dioxygen Inorganic materials 0.000 claims description 3
- 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 claims 3
- 239000000693 micelle Substances 0.000 claims 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 4
- HUVSVEZKLBFKTA-UHFFFAOYSA-N [Ca].[W] Chemical compound [Ca].[W] HUVSVEZKLBFKTA-UHFFFAOYSA-N 0.000 abstract 1
- 229910052727 yttrium Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 19
- 229910004298 SiO 2 Inorganic materials 0.000 description 17
- 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 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- 229910001960 metal nitrate Inorganic materials 0.000 description 10
- 229910000667 (NH4)2Ce(NO3)6 Inorganic materials 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 9
- 229910002027 silica gel Inorganic materials 0.000 description 9
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 239000012752 auxiliary agent Substances 0.000 description 7
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTDQFVRSJWCWNK-UHFFFAOYSA-N [Fe].[Bi].[Mo] Chemical compound [Fe].[Bi].[Mo] DTDQFVRSJWCWNK-UHFFFAOYSA-N 0.000 description 2
- OTKOPKDCLGDHFV-UHFFFAOYSA-N azane;2-methylprop-1-ene Chemical compound N.CC(C)=C OTKOPKDCLGDHFV-UHFFFAOYSA-N 0.000 description 2
- GLAKNHGQBRSLIO-UHFFFAOYSA-N azane;prop-1-ene Chemical group N.CC=C GLAKNHGQBRSLIO-UHFFFAOYSA-N 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 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
- 239000000463 material Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010909 process residue Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- PDNNQADNLPRFPG-UHFFFAOYSA-N N.[O] Chemical compound N.[O] PDNNQADNLPRFPG-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- BYUANIDVEAKBHT-UHFFFAOYSA-N [Mo].[Bi] Chemical compound [Mo].[Bi] BYUANIDVEAKBHT-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910000147 aluminium phosphate 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
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- NWJZFGOFYNPABH-UHFFFAOYSA-N prop-1-ene;prop-2-enenitrile Chemical compound CC=C.C=CC#N NWJZFGOFYNPABH-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A catalyst comprising a complex of catalytic oxides comprising rubidium, cerium, chromium, iron, bismuth, molybdenum, and at least one of nickel or nickel and cobalt, optionally magnesium, and optionally one of phosphorus, antimony, tellurium, sodium, lithium, potassium, cesium, thallium, boron, germanium, tungsten calcium, wherein the relative ratios of these elements are represented by the following general formula: RbaCebCrcMgdAeFefBigYhMo12Ox wherein A is Ni or the combination of Ni and Co, Y is at least one of P, Sb, Te, Li, Na, K, Cs, Tl, B, Ge, W, Ca, Zn, a rare earth element, or mixtures thereof, a is about 0.01 to about 1, b is about 0.01 to about 3, c is about 0.01 to about 2, d is 0 to about 7, e is about 0.01 to about 10, f is about 0.01 to about 4, g is about 0.05 to about 4, h is 0 to about 3, x is a number determined by the valence requirements of the other elements present, wherein b+c is greater than g and wherein the catalyst is substantially free of manganese, a noble metal and vanadium. The catalyst is useful in processes for the ammoxidation of an olefin selected from the group consisting of propylene, isobutylene or mixtures thereof, to acrylonitrile, methacrylonitrile and mixtures thereof, respectively.
Description
The present invention relates to a kind of improvement catalyst that the unsaturated hydrocarbons ammoxidation is corresponding unsaturated nitrile that is used for.Particularly, the present invention relates to propylene and/or isobutene ammonia oxidizing is improving one's methods of acrylonitrile and/or methacrylonitrile and catalyst.More specifically, the present invention relates to a kind of novel, improved ammoxidation catalyst, the catalytic oxidation thing mixture comprising at least a in iron, bismuth, molybdenum, magnesium, cobalt or the nickel, rubidium, cerium and chromium does not contain manganese, noble metal and vanadium substantially.
DESCRIPTION OF THE PRIOR ART
For a long time, the catalyst that comprises iron, bismuth and molybdenum and suitable auxiliary agents is used to propylene and transforms when existing at high temperature and ammonia oxygen (being generally air form), makes acrylonitrile.Particularly, BP GB1436475 and U.S. Pat 4,766,232,4,377,534,4,040,978,4,168,246,5,223,469 and 4,863,891 all relate to bismuth-molybdenum-iron catalyst, are auxiliary agent with II family element wherein, produce acrylonitrile.In addition, United States Patent (USP) 4,190,608 disclose similarly be used for olefin oxidation contain auxiliary agent bismuth-molybdenum-iron catalyst.United States Patent (USP) 5,093,299,5,212,137,5,658,842 and 5,834,394 relate to a kind of auxiliary agent bismuth-molybdenum catalyst that contains, and have higher acrylonitrile productive rate.
The objective of the invention is a kind of new catalyst that comprises unique auxiliary agent combination, it has preferable performance in the reaction that propylene, isobutene or its mixture through catalytic ammoxidation are acrylonitrile, methacrylonitrile or its mixture.
Summary of the invention
The present invention relates to propylene and/or isobutene ammonia oxidizing is the improvement catalyst and the method for acrylonitrile and/or methacrylonitrile.
In a specific embodiment, the present invention is the catalyst that comprises catalytic oxidation thing mixture, at least a comprising in rubidium, cerium, chromium, magnesium, iron, bismuth, molybdenum and nickel or nickel and the cobalt, and the ratio of these elements is illustrated in the following general formula.
Rb
aCe
bCr
cMg
dA
eFe
fBi
gMo
12O
x
Wherein, A is the combination of Ni or Ni and Co,
A be about 0.01～about 1,
B be about 0.01～about 3,
C be about 0.01～about 2,
D be about 0.01～about 7,
E be about 0.01～about 10,
F be about 0.01～about 4,
G be about 0.05～about 4,
X is the numerical value that other element valence determined,
Wherein, b+c＞g, and catalyst does not contain manganese, noble metal or vanadium substantially.
In second specific embodiment, the present invention is the catalyst that comprises catalytic oxidation thing mixture, comprising at least a in rubidium, cerium, chromium, magnesium, iron, bismuth, molybdenum and nickel or nickel and the cobalt, optional comprise in phosphorus, antimony, tellurium, sodium, lithium, potassium, caesium, thallium, boron, tungsten, the calcium a kind ofly, the ratio of these elements is illustrated in the following general formula.
Rb
aCe
bCr
cMg
dA
eFe
fBi
gY
hMo
12O
x
Wherein, A is the combination of Ni or Ni and Co,
Y is at least a or its mixture in P, Sb, Te, Li, Na, K, Cs, Tl, B, Ge, W, Ca, Zn, the rare earth element,
A be about 0.01～about 1,
B be about 0.01～about 3,
C be about 0.01～about 2,
D be about 0.01～about 7,
E be about 0.01～about 10,
F be about 0.01～about 4,
G be about 0.05～about 4,
H is 0～about 3,
X is the numerical value that other element valence determined,
Wherein, b+c＞g, and catalyst does not contain manganese, noble metal or vanadium substantially.
In the 3rd specific embodiment, the present invention is the catalyst that comprises catalytic oxidation thing mixture, comprising at least a in rubidium, cerium, chromium, iron, bismuth, molybdenum and nickel or nickel and the cobalt, optional comprise in phosphorus, antimony, tellurium, sodium, lithium, potassium, caesium, thallium, boron, tungsten, the calcium a kind ofly, the ratio of these elements is illustrated in the following general formula.
Rb
aCe
bCr
cA
eFe
fBi
gY
hMo
12O
x
Wherein, A is the combination of Ni or Ni and Co,
Y is at least a or its mixture in P, Sb, Te, Li, Na, K, Cs, Tl, B, Ge, W, Ca, Zn, the rare earth element,
A be about 0.01～about 1,
B be about 0.01～about 3,
C be about 0.01～about 2,
E be about 0.01～about 10,
F be about 0.01～about 4,
G be about 0.05～about 4,
H is 0～about 3,
The numerical value that x is determined for other element valence requirement,
Wherein, b+c＞g, and catalyst does not contain manganese, noble metal or vanadium substantially.
The alkene that the present invention also relates to be selected from propylene, isobutene or its mixture is converted into the method for acrylonitrile, methacrylonitrile and its mixture, described alkene is on mixed metal oxide catalyst, react with the molecular oxygen that contains gas and ammonia in the high temperature gas phase, wherein catalyst is top described catalyst.
Detailed Description Of The Invention
The present invention is a kind of new catalyst, and it comprises unique combination and auxiliary agent ratio, is that acrylonitrile, methacrylonitrile and its mixture have preferable performance to propylene, isobutene or its mixture through catalytic ammoxidation.
A specific embodiment of the present invention relates to the ammoxidation catalyst that comprises oxide mixture, and comprising at least a in rubidium, cerium, chromium, magnesium, iron, bismuth, molybdenum and nickel or nickel and the cobalt, the ratio of these elements is illustrated in the following general formula.
Rb
aCe
bCr
cMg
dA
eFe
fBi
gMo
12O
x
Wherein, A is Ni or Ni and Co combination,
A be about 0.01～about 1,
B be about 0.01～about 3,
C be about 0.01～about 2,
D be about 0.01～about 7,
E be about 0.01～about 10,
F be about 0.01～about 4,
G be about 0.05～about 4,
The numerical value that x is determined for other element valence requirement,
Wherein, b+c＞g, and catalyst does not contain manganese, noble metal or vanadium substantially.In another embodiment, b is also greater than c.In another specific embodiment of the present invention, a is 0.05～0.3.
In another embodiment, the present invention relates to comprise the catalyst of catalytic oxidation thing mixture, comprising at least a in rubidium, cerium, chromium, iron, bismuth, molybdenum and nickel or nickel and the cobalt, optional comprise magnesium and optionally comprise in phosphorus, antimony, tellurium, sodium, lithium, potassium, caesium, thallium, boron, germanium, tungsten, the calcium a kind ofly that the ratio of these elements is illustrated in the following general formula.
Rb
aCe
bCr
cMg
dA
eFe
fBi
gY
hMo
12O
x
Wherein, A is Ni or Ni and Co combination,
Y is at least a or its mixture in P, Sb, Te, Li, Na, K, Cs, Tl, B, Ge, W, Ca, Zn, the rare earth element,
A be about 0.01～about 1,
B be about 0.01～about 3,
C be about 0.01～about 2,
D is 0～7, be preferably about 0.01～about 7,
E be about 0.01～about 10,
F be about 0.01～about 4,
G be about 0.05～about 4,
H is 0～about 3,
The numerical value that x is determined for other element valence requirement,
Wherein, b+c＞g, and catalyst does not contain manganese, noble metal or vanadium substantially.In another embodiment, b is also greater than c.In another specific embodiment of the present invention, a is 0.05～0.3.
In above-mentioned carbon monoxide-olefin polymeric, the amount of cerium+chromium (calculating with atom) (is b+c＞g) greater than the amount of bismuth.If less than the amount of bismuth, activity of such catalysts is just bad for the amount of cerium+chromium (calculating with atom).In another specific embodiment, the amount of cerium (calculating with atom) (is b＞c) greater than the amount of chromium.
At least a hopcalite in oxide that basic carbon monoxide-olefin polymeric described here is rubidium, cerium, chromium, magnesium, iron, bismuth, molybdenum and nickel or nickel and the cobalt.Except that the element of clearly getting rid of, also can comprise other element or auxiliary agent.In a specific embodiment, catalyst comprises in phosphorus, antimony, tellurium, sodium, lithium, potassium, caesium, thallium, boron, germanium, tungsten, calcium, zinc and the rare earth element (La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, one of Tm or Yb) one or more.
In addition, propylene, ammonia and oxygen are converted into acrylonitrile, comprise some element the higher acrylonitrile productive rate of catalyst acquisition is harmful to.They are manganese, noble metal (noble metal refers to ruthenium, rhodium, palladium, osmium, iridium and platinum here) and vanadium.Catalyst comprises noble metal can make ammonia generation oxidation, thereby reduces the required effective ammonia amount of acrylonitrile that produces.Vanadium makes activity of such catalysts expect that product selectivity is bad too by force, thereby produces more oxycarbide (COx) and less acrylonitrile.Catalyst contains manganese can make the acrylonitrile productive rate reduce.Therefore catalyst of the present invention does not contain manganese, noble metal and/or vanadium substantially.Here for manganese and vanadium, " not containing substantially " refers to that atomic ratio with molybdenum was less than 0.2: 12.For noble metal, " not containing substantially " refers to that atomic ratio with molybdenum was less than 0.005: 12.Preferably, catalyst does not contain manganese, noble metal and/or vanadium.
Catalyst of the present invention can be load, also can be unsupported (being that catalyst can comprise carrier).Suitable carriers is silica, aluminium oxide, zirconia, titanium oxide or its mixture.Typically, carrier plays a part adhesive, forms harder, more wear-resisting catalyst.Yet in the commercial Application, suitable between active phase (being above-mentioned catalytic oxidation thing mixture) and the carrier to mix obtaining acceptable catalyst activity and intensity (wear-resisting) be vital.Usually trend is, improves active phase content and can improve catalyst activity, but reduce catalyst strength.Typically, in the supported catalyst, vector contg is 40～60wt.%.In a specific embodiment of the present invention, the vector contg that supported catalyst comprises arrives about 30wt.% less.In another embodiment of the present invention, the vector contg that supported catalyst comprises is up to about 70wt.%.Can comprise one or more auxiliary elements in the available carrier material, contain sodium (Na) as silica gel, these auxiliary elements mix in the catalyst by carrier material.
In a specific embodiment, the catalyst silica gel load.If the silica gel colloid diameter is too little, the surface area of obtained catalyst can improve, and selection of catalysts is just relatively poor.If the silica gel colloid diameter is too big, then the scuff resistance of obtained catalyst is just poor.Typically, the average colloid diameter of silica gel is about 15nm～about 50nm.In a specific embodiment of the present invention, the about 10nm of average colloid diameter of silica gel can be little of about 8nm.In another embodiment of the present invention, the about 100nm of average colloid diameter of silica gel.In another specific embodiment of the present invention, the about 20nm of average colloid diameter of silica gel.
Preparation of catalysts can be with any preparation method known to those skilled in the art among the present invention.For example, carry out co-precipitation, the preparation catalyst with various precipitating reagents.After the co-precipitation, dry, grind and be suitable size.Alternatively, the co-precipitation material can be paste-like, carries out spray-drying according to conventional method then.Catalyst can push into bead or in oil and form the lance shape, as known in the art.The detailed process of preparation catalyst is found in U.S. Pat 5,093,299; 4,863,891 and 4,766,232, be hereby incorporated by.In a specific embodiment, catalytic component is paste-like with carrier and mixes, and is dry then, perhaps catalytic component is immersed on silica or other carrier.
Bismuth is introduced catalyst with the oxide or the form that can generate the salt of oxide through roasting.The preferred water-soluble salt that disperses, forms steady oxide through heat treatment that adopts easily.Particularly preferred bismuth source is a bismuth nitrate.
The iron component can obtain from the iron compound that forms oxide after roasting in the catalyst.The same with other element, preferred water dissolved salt, easy so evenly dispersion in catalyst.Ferric nitrate more preferably.
Molybdenum component is from any molybdenum oxide in the catalyst.Yet the molybdenum salt of preferred hydrolyzable or decomposition is as the molybdenum source.Most preferred raw material is an ammonium molybdate.
In the catalyst other must component and optional components (as Ni, Co, Mg, Cr, P, Sn, Te, B, Ge, Zn, In, Ca, W or its mixture) can be from any suitable source.For example, cobalt, nickel and magnesium can be introduced catalyst with nitrate.In addition, also available insoluble carbonate or the hydroxide that after heat treatment forms oxide of magnesium is introduced catalyst.The introducing available bases slaine of phosphorus or alkali salt or ammonium salt, but preferably adopt phosphoric acid.
In the catalyst essential and optional basic component (as Rb, Li, Na, K, Cs, Tl or its mixture) can oxide or the form that after roasting, forms the salt of oxide introduce catalyst.The preferred salt that uses mixes catalyst with these elements, for example obtains easily and easily molten nitrate.
During the preparation catalyst, typically the aqueous solution with ammonium heptamolybdate mixes with silica gel, adds and contains the slurry that other element compound is preferably nitrate.Then with solid matter oven dry, denitrogenation and roasting.Preferably, catalyst carries out spray-drying under 110 ℃～350 ℃, is preferably 110 ℃～250 ℃, more preferably 110 ℃～180 ℃.Denitrification temperature is 100 ℃～500 ℃, is preferably 250 ℃～450 ℃.At last, sintering temperature is 300 ℃～700 ℃, is preferably 350 ℃～650 ℃.
Catalyst of the present invention is used for method for ammoxidation, the alkene that is selected from propylene, isobutene or its mixture is converted into acrylonitrile, methacrylonitrile and its mixture, wherein said alkene reacts with the molecular oxygen that contains gas and ammonia in the gas phase of HTHP when catalyst exists.
Though can envision the reactor such as the carrier pipe reactor that adopt other type, preferably, ammoxidation reaction carries out in flowing bed reactor.Flowing bed reactor is used to make acrylonitrile and is known by prior art.For example, U.S. Pat 3,230, the 246 reactor designs that proposed just are fit to, and are hereby incorporated by.
The condition that ammoxidation reaction carries out is also known by prior art, as U.S. Pat 5,093,299; 4,863,891; 4,767,878 and 4,503,001 proposition is hereby incorporated by.Typically, the ammoxidation process is that propylene or isobutene are contacted with fluid catalyst when ammonia exists with oxygen, at high temperature generates acrylonitrile or methacrylonitrile.Can use the oxygen in any source.But, preferably use air from considering economically.Typical oxygen and olefin molar ratio are 0.5: 1～4: 1 in the raw material, are preferably 1: 1～3: 1.
The ammonia of raw material and olefin molar ratio can change between 0.5: 1～2: 1 in the reaction.Ammonia-olefin ratios does not have the upper limit in fact, but from economic consideration, generally has no reason above 2: 1.From the production of propylene acrylonitrile, the proper raw material ratio is 0.9: 1～1.3: 1 an ammonia propylene ratio, and 8.0: 1～12.0: 1 air propylene ratio with catalyst of the present invention.Catalyst of the present invention can obtain higher acrylonitrile productive rate about 1: 1～about 1.05: 1 hanging down under the ammonia propylene ratio.Should " low ammonia condition " help to reduce unreacted ammonia in the reactor discharging, thereby help to reduce process residue subsequently, this condition is called " ammonia penetrates ".Particularly, must before recover acrylonitrile, unreacted ammonia be removed from the reactor discharging.Typically, contact generation ammonium sulfate with sulfuric acid or contact generation acrylic acid ammonia, unreacted ammonia is removed, either way can produce the process residue that needs processing and/or dispose with acrylic acid by the reactor discharging.
The temperature that reaction is carried out is about 260 ℃～600 ℃, is preferably 310 ℃～500 ℃, is preferably 350 ℃～480 ℃ especially.Though time of contact is inessential, be generally 0.1～50s, be preferably 1～15s.
The recovery of product and purification can be adopted any method known to those skilled in the art.A kind of method comprises give vent to anger body and function cold water or suitable solvent of reactor stream purified, thereby shifts out product, distills purification then.
The main application of catalyst of the present invention is that to be used for ammoxidation of propylene be acrylonitrile.But it is acrylic acid that this catalyst also can be used for propylene oxidation.This technology is typically two-stage process, and wherein propylene mainly is converted into methacrylaldehyde when one section catalyst exists, and methacrylaldehyde mainly is converted into acrylic acid again on two sections catalyst.Catalyst described here is applicable to that one section propylene oxidation is a methacrylaldehyde.The detailed specific embodiment
In order to illustrate the present invention, prepared catalyst of the present invention, also prepared the similar catalyst that lacks one or more elements or comprise the element that the generation acrylonitrile is harmful in addition, under condition of similarity, they are estimated then.These embodiment are the usefulness for illustrating only.
Preparation of Catalyst
Embodiment 1:
Catalyst 50wt%Ni
5.0Mg
2.0Fe
1.8Bi
0.45Ce
0.9Cr
0.1Rb
0.15Mo
12O
48.4+ 50wt%SiO
2Preparation process as follows: with metal nitrate Fe (NO in order
3)
3.9H
2O (69.752g), Ni (NO
3)
2.6H
2O (139.458g), Mg (NO
3)
2.6H
2O (49.186g), Bi (NO
3)
3.5H
2O (20.937g), RbNO
3(2.122g) reach (NH
4)
2Ce (NO
3)
6(94.654g 50% solution) is dissolved in the 1000ml beaker under～70 ℃ together.(AHM) (203.219g) is dissolved in the 310ml distilled water with ammonium heptamolybdate.With the CrO that is dissolved in the 20ml water
3(0.959g) add this solution.Add silica (871.08g 28.75% SiO then
2Colloidal sol), add metal nitrate again.Then the yellow slurry that forms is carried out spray-drying.Material denitrogenation to obtaining under 290 ℃/3h and 425 ℃/3h condition, roasting 3 hours in 570 ℃ of following air then.
Embodiment 2:
50wt％Ni
2.5Mg
2.0Co
2.5Fe
1.8Bi
0.45Ce
0.9Cr
0.1Rb
0.15MO
12O
48.4+50wt％SiO
2
This Preparation of catalysts is as embodiment 1.Catalyst formulation is as follows: Fe (NO
3)
3.9H
2O (69.737g), Ni (NO
3)
2.6H
2O (69.714g), Mg (NO
3)
2.6H
2O (49.176g), Co (NO
3)
2.6H
2O (69.774g), Bi (NO
3)
3.5H
2O (20.993g), RbNO
3(2.121g) reach (NH
4)
2Ce (NO
3)
6(94.634g 50% solution) is dissolved in the 1000ml beaker under～70 ℃ together.(AHM) (203.175g) is dissolved in the 310ml distilled water with ammonium heptamolybdate.With the CrO that is dissolved in the 20ml water
3(0.959g) add this solution.Add silica (796.178g 31.4%SiO then
2Colloidal sol), add metal nitrate again.
Embodiment 3:
50wt％Ni
5.0Mg
2.0Fe
1.8Bi
0.45Ce
0.9Cr
0.1Li
0.3Rb
0.15Mo
12O
48.55+50wt％SiO
2
This Preparation of catalysts is as embodiment 1.Catalyst formulation is as follows: Fe (NO
3)
3.9H
2O (69.632g), Ni (NO
3)
2.6H
2O (139.219g), Mg (NO
3)
2.6H
2O (49.102g), LiNO
3(1.981g), Bi (NO
3)
3.5H
2O (20.901g), RbNO
3(2.118g) reach (NH
4)
2Ce (NO
3)
6(94.634g 50% solution) is dissolved in the 1000ml beaker under～70 ℃ together.(AHM) (202.87g) is dissolved in the 310ml distilled water with ammonium heptamolybdate.With the CrO that is dissolved in the 20ml water
3(0.958g) add this solution.Add silica (796.178g 31.4%SiO then
2Colloidal sol), add metal nitrate again.
Embodiment 4:
50wt％Ni
2.5Mg
2.0Co
2.5Fe
1.8Bi
0.45Ce
0.9Cr
0.1P
0.1W
0.1Rb
0.15Mo
12O
48.95+50wt％SiO
2
This Preparation of catalysts is as embodiment 1.Catalyst formulation is as follows: Fe (NO
3)
3.9H
2O (68.936g), Ni (NO
3)
2.6H
2O (68.914g), Mg (NO
3)
2.6H
2O (48.611g), Co (NO
3)
2.6H
2O (68.973g), Bi (NO
3)
3.5H
2O (20.693g), RbNO
3(2.097g) reach (NH
4)
2Ce (NO
3)
6(93.547g 50% solution) is dissolved in the 1000ml beaker under～70 ℃ together.(AHM) (200.842g) is dissolved in the 310ml distilled water with ammonium heptamolybdate.With H
3PO
4(1.093g 85% solution), (NH
4)
6H
2W
12O
40(2.388g) and be dissolved in CrO in the 20ml water
3(0.948g) add this solution.Add silica (796.178g 31.4%SiO then
2Colloidal sol), add metal nitrate again.
Embodiment 5:
50wt％Ni
5.0Mg
2.0Fe
1.8Bi
0.45Ce
0.9Cr
0.1Na
0.2Rb
0.15Mo
12O
48.5+50wt％SiO
2
This Preparation of catalysts is as embodiment 1.Catalyst formulation is as follows: Fe (NO
3)
3.9H
2O (69.586g), Ni (NO
3)
2.6H
2O (139.127g), Mg (NO
3)
2.6H
2O (49.07g), NaNO
3(1.626g), Bi (NO
3)
3.5H
2O (20.888g), RbNO
3(2.117g) reach (NH
4)
2Ce (NO
3)
6(94.429g 50% solution) is dissolved in the 1000ml beaker under～70 ℃ together.(AHM) (202.736g) is dissolved in the 310ml distilled water with ammonium heptamolybdate.With the CrO that is dissolved in the 20ml water
3(0.957g) add this solution.Add silica (796.178g 31.4%SiO then
2Colloidal sol), add metal nitrate again.
Embodiment 6:
50wt％Ni
5.0Mg
2.0Fe
1.8Bi
0.45Ce
0.9Cr
0.1P
0.1Rb
0.15Mo
12O
48.65+50wt％SiO
2
This Preparation of catalysts is as embodiment 1.Catalyst formulation is as follows: Fe (NO
3)
3.9H
2O (69.562g), Ni (NO
3)
2.6H
2O (139.079g), Mg (NO
3)
2.6H
2O (49.053g), Bi (NO
3)
3.5H
2O (20.881g), RbNO
3(2.097g) reach (NH
4)
2Ce (NO
3)
6(94.397g 50% solution) is dissolved in the 1000ml beaker under～70 ℃ together.(AHM) (202.667g) is dissolved in the 310ml distilled water with ammonium heptamolybdate.With H
3PO
4(1.103g85% solution) and be dissolved in CrO in the 20ml water
3(0.957g) add this solution.Add silica (796.178g 31.4%SiO then
2Colloidal sol), add metal nitrate again.
Comparative Examples A～D:
A.50wt％Ni
5.0Mg
2.0Fe
1.8Bi
0.45Ce
0.9Rb
0.15Mo
12O
48.25+50wt％SiO
2
B.50wt％Ni
5.0Mg
2.0Fe
1.8Bi
0.45Cr
0.1Rb
0.15Mo
12O
46.6+50wt％SiO
2
C.50wt％Ni
5.0Mg
2.0Fe
1.8Bi
0.45Ce
0.9Cr
0.1K
0.15Mo
12O
48.4+50wt％SiO
2
D.50wt％Ni
5.0Mg
2.0Fe
1.8Bi
0.45Ce
0.9Cr
0.1Cs
0.15Mo
12O
48.4+50wt％SiO
2
Adopt embodiment 1 described preparation method, prepare other several catalyst that do not contain in chromium, cerium, the rubidium one or more similarly.In comparative example C and D, respectively with caesium (CsNO
3, 2.797g) and potassium (KNO
3, 1.458g) replace with rubidium.
Comparative example E:
50wt％Ni
5.0Mg
2.0Fe
1.8Bi
0.45Ce
0.9Cr
0.1Rb
0.15Mn
1.0Mo
12O
49.4+50wt％SiO
2
This catalyst has added manganese Mn (NO by embodiment 1 preparation the time
3)
2(32.699g 51.1% solution).
Comparative example F:
50wt％Ni
5.0Mg
2.0Fe
1.8Bi
0.45Ce
0.9Cr
0.1Rb
0.15Pd
0.1Mo
12O
48.5+50wt％SiO
2
This catalyst has added precious metal palladium Pd (NO by embodiment 1 preparation the time
3)
2(2.2g).
Comparative example G:
50wt％Ni
5.0Mg
2.0Fe
1.8Bi
0.45Ce
0.9Cr
0.1Rb
0.15V
0.5Mo
12O
49.65+50wt％SiO
2
This catalyst has added vanadium NH by embodiment 1 preparation the time
4VO
3(5.514g).
Comparative example H:
50wt％Ni
5.0Mg
2.0Fe
1.8Bi
0.45Ce
0.15Cr
0.3Rb
0.15Mo
12O
47.2+50wt％SiO
2
This Preparation of catalysts is as embodiment 1.Calculate but press atom, the molal quantity of cerium+chromium equals the molal quantity of bismuth.Catalyst formulation is as follows: Fe (NO
3)
3.9H
2O (72.939g), Ni (NO
3)
2.6H
2O (145.83g), Mg (NO
3)
2.6H
2O (51.434g), Bi (NO
3)
3.5H
2O (21.894g), RbNO
3(2.219g) reach (NH
4)
2Ce (NO
3)
6(16.496g 50% solution) is dissolved in the 1000ml beaker under～70 ℃ together.(AHM) (212.504g) is dissolved in the 310ml distilled water with ammonium heptamolybdate.With the CrO that is dissolved in the 20ml water
3(3.009g) add this solution.Add silica (871.08g 28.75%SiO then
2Colloidal sol), add metal nitrate again.
Comparative example I:
50wt％Ni
5.0Mg
2.0Fe
1.8Bi
0.45Ce
0.1Cr
0.1Rb
0.15Mo
12O
46.8+50wt％SiO
2
This Preparation of catalysts is as embodiment 1.Calculate but press atom, the number of cerium+chromium is less than the number of bismuth.Catalyst formulation is as follows: Fe (NO
3)
3.9H
2O (73.642g), Ni (NO
3)
2.6H
2O (147.236g), Mg (NO
3)
2.6H
2O (51.93g), Bi (NO
3)
3.5H
2O (22.105g), RbNO
3(2.24g), (NH
4)
2Ce (NO
3)
6(11.104g 50% solution) is dissolved in the 1000ml beaker under～70 ℃ together.(AHM) (214.553g) is dissolved in the 310ml distilled water with ammonium heptamolybdate.With the CrO that is dissolved in the 20ml water
3(1.013g) add this solution.Add silica (871.08g 28.75%SiO then
2Colloidal sol), add metal nitrate again.
Comparative example J:
50wt％Ni
5.0Mg
2.0Fe1
.8Bi
2.0Ce
0.9Cr
0.1Rb
0.15Mo
12O4
6.8+50wt％SiO
2
This Preparation of catalysts is as embodiment 1.Calculate but press atom, the number of cerium+chromium is less than the number of bismuth.Catalyst formulation is as follows: Fe (NO
3)
3.9H
2O (61.264g), Ni (NO
3)
2.6H
2O (122.488g), Mg (NO
3)
2.6H
2O (43.201g), Bi (NO
3)
3.5H
2O (81.732g), RbNO
3(1.863g) reach (NH
4)
2Ce (NO
3)
6(83.136g 50% solution) is dissolved in the 1000ml beaker under～70 ℃ together.(AHM) (178.49g) is dissolved in the 310ml distilled water with ammonium heptamolybdate.With the CrO that is dissolved in the 20ml water
3(0.843g) add this solution.Add silica (871.08g 28.75%SiO then
2Colloidal sol), add metal nitrate again.
Evaluating catalyst
All evaluation tests are all carried out in the 40cc fluidized-bed reactor.Propylene enters reactor with the speed of 0.06WWH (be propylene weight/catalyst weight/hour).Reactor pressure maintains 10psig.Temperature of reactor is 430 ℃.Behind stable～20h, the collecting reaction product sample.The reactor discharging is collected in the bubble type clarifier that contains cold HCl solution.Measure the tail gas flow velocity with soap-foam flowmeter, form with the terminal tail gas of the gas Chromatographic Determination that the splitter gas analyser is housed.After reclaim finishing, with whole clarifier liquid with distilled water diluting to about 200gms.With the interior mark of the 2-butanone of having weighed as the 50g dilute solution.In GC, analyze 2 μ l samples with hydrogen flame ion detector and Carbowax post.NH
3The mensuration of amount adopts the method for the superfluous HCl of NaOH titration.Following embodiment illustrates the present invention.
Table 1
| Embodiment | Active phase composition | Total C 3 ＝Conversion ratio | The AN conversion ratio | The AN selectivity |
| 1 | Ni 5.0Mg 2.0Fe 1.8Bi 0.45Ce 0.9Cr 0.1Rb 0.15Mo 12O 48.4 | 98.8 | 80.0 | 81.0 |
| 2 | Ni 2.5Mg 2.0Co 2.5Fe 1.8Bi 0.45Ce 0.9Cr 0.1Rb 0.15Mo 12O 48.4 | 99.2 | 81.8 | 82.5 |
| 3 | Ni 5.0Mg 2.0Fe 1.8Bi 0.45Ce 0.9Cr 0.1Li 0.3Rb 0.15Mo 12O 48.55 | 98.8 | 79.9 | 81.4 |
| 4 | Ni 2.5Mg 2.0Co 2.5Fe 1.8Bi 0.45Ce 0.9Cr 0.1P 0.1W 0.1Rb 0.15Mo 12O 48.95 | 99.7 | 80.9 | 81.2 |
| 5 | Ni 5.0Mg 2.0Fe 1.8Bi 0.45Ce 0.9Cr 0.1Na 0.2Rb 0.15Mo 12O 48.5 | 99.6 | 81.0 | 81.3 |
| 6 | Ni 5.0Mg 2.0Fe 1.8Bi 0.45Ce 0.9Cr 0.1P 0.1Rb 0.15Mo 12O 48.65 | 99.6 | 82.3 | 82.6 |
| A | Ni 5.0Mg 2.0Fe 1.8Bi 0.45Ce 0.9Rb 0.15Mo 12O 48.25 | 99.4 | 79.3 | 79.9 |
| B | Ni 5.0Mg 2.0Fe 1.8Bi 0.45Cr 0.1Rb 0.15Mo 12O 46.6 | 91.2 | 75.8 | 83.1 |
| C | Ni 5.0Mg 2.0Fe 1.8Bi 0.45Ce 0.9Cr 0.1K 0.15Mo 12O 48.4 | 99.7 | 77.6 | 77.8 |
| D | Ni 5.0Mg 2.0Fe 1.8Bi 0.45Ce 0.9Cr 0.1Cs 0.15Mo 12O 48.4 | 96.8 | 69.6 | 72.0 |
| E | Ni 5.0Mg 2.0Fe 1.8Bi 0.45Ce 0.9Cr 0.1Rb 0.15Mn 1.0Mo 12O 49.4 | 97.3 | 78.0 | 78.6 |
| F | Ni 5.0Mg 2.0Fe 1.8Bi 0.45Ce 0.9Cr 0.1Rb 0.15Pd 0.1Mo 12O 48.5 | 99.3 | 78.7 | 81.4 |
| G | Ni 5.0Mg 2.0Fe 1.8Bi 0.45Ce 0.9Cr 0.1Rb 0.15V 0.5Mo 12O 49.65 | 96.4 | 76.8 | 79.7 |
| H | Ni 5.0Mg 2.0Fe 1.8Bi 0.45Ce 0.15Cr 0.3Rb 0.15Mo 12O 47.2 | 93.5 | 77.9 | 83.3 |
| I | Ni 5.0Mg 2.0Fe 1.8Bi 0.45Ce 0.1Cr 0.1Rb 0.15Mo 12O 46.8 | 94.9 | 74.4 | 78.5 |
| J | Ni 5.0Mg 2.0Fe 1.8Bi 2.0Ce 0.9Cr 0.1Rb 0.15Mo 12O 46.8 | 97.7 | 78.8 | 80.7 |
Annotate:
1. the catalyst of all evaluations all contains 50% mutually active and 50%SiO
2
2. " Total C
3 =Conv. " be the molar content that is converted into the propylene of whole products.
3. " Conv.to AN " is the molar content that is converted into the propylene of acrylonitrile.
4. " Sel.to AN " is the molar percentage of the propylene of the acrylonitrile that produces and conversion.
It is at least a that the unique distinction of carbon monoxide-olefin polymeric of the present invention is that it comprises in rubidium, cerium, chromium, magnesium, iron, bismuth, molybdenum and cobalt or the nickel, do not contain manganese, noble metal or vanadium substantially.The element combinations of ratio described here was not used in single ammoxidation catalyst general formula.As shown in table 1, be acrylonitrile for ammoxidation of propylene, catalyst of the present invention shows more performance than the catalyst that comprises similar (but incomplete same) element combinations in the prior art patent.More specifically, compare with the catalyst outside category of the present invention, comprise that at least a and catalyst that do not contain manganese, noble metal or vanadium substantially in rubidium, cerium, chromium, magnesium, iron, bismuth, molybdenum and cobalt or the nickel had both had higher total propylene conversion and had been converted into the conversion ratio of acrylonitrile, had higher acrylonitrile selectivity again.
Though the above-mentioned explanation and the specific embodiment are typical for the present invention's practice, significantly, concerning with this explanation those of ordinary skill in the related art, many selections, modification and change all are conspicuous.Therefore, all these are selected, modify and change and all have a mind to be contained in and fall in the spirit and wide in range category of claims.
Claims (24)
1. carbon monoxide-olefin polymeric that comprises catalytic oxidation thing compound, it comprises at least a in rubidium, cerium, chromium, magnesium, iron, bismuth, molybdenum and nickel or nickel and the cobalt, wherein the relative scale of these elements is represented with following general formula
Rb
aCe
bCr
cMg
dA
eFe
fBi
gMo
12O
x
Wherein, A is the combination of Ni or Ni and Co,
A be about 0.01～about 1,
B be about 0.01～about 3,
C be about 0.01～about 2,
D be about 0.01～about 7,
E be about 0.01～about 10,
F be about 0.01～about 4,
G be about 0.05～about 4,
The numerical value that x is determined for other element valence requirement,
Wherein, b+c＞g, and catalyst does not contain manganese, noble metal or vanadium substantially.
2. by the described carbon monoxide-olefin polymeric of claim 1, wherein b is less than c.
3. by the described carbon monoxide-olefin polymeric of claim 1, wherein catalyst comprises phosphorus.
4. by the described carbon monoxide-olefin polymeric of claim 1, wherein catalyst comprises at least a or its mixture in potassium, caesium, the sodium.
5. by the described carbon monoxide-olefin polymeric of claim 1, wherein carbon monoxide-olefin polymeric comprises the carrier that is selected from silica, aluminium oxide, zirconia, titanium oxide or its mixture.
6. by the described carbon monoxide-olefin polymeric of claim 5, wherein carrier is about 30wt%～70wt% of catalyst.
7. by the described carbon monoxide-olefin polymeric of claim 1, wherein carbon monoxide-olefin polymeric comprises that average micelle size is the silica of about 8nm～about 100nm.
8. carbon monoxide-olefin polymeric that comprises catalytic oxidation thing compound, it comprises at least a in rubidium, cerium, chromium, iron, bismuth, molybdenum and nickel or nickel and the cobalt, optional comprise magnesium and optionally comprise a kind of in phosphorus, antimony, tellurium, sodium, lithium, potassium, caesium, thallium, boron, germanium, tungsten, the calcium that the relative scale of these elements is represented with following general formula.
Rb
aCe
bCr
cMg
dA
eFe
fBi
gY
hMo
12O
x
Wherein, A is the combination of Ni or Ni and Co,
Y is at least a or its mixture in P, Sb, Te, Li, Na, K, Cs, Tl, B, Ge, W, Ca, Zn, the rare earth element,
A be about 0.01～about 1,
B be about 0.01～about 3,
C be about 0.01～about 2,
D is 0～7,
E be about 0.01～about 10,
F be about 0.01～about 4,
G be about 0.05～about 4,
H is 0～about 3,
The numerical value that x is determined for other element valence requirement,
Wherein, b+c＞g, and catalyst does not contain manganese, noble metal or vanadium substantially.
9. by the described carbon monoxide-olefin polymeric of claim 8, wherein b is less than c.
10. by the described carbon monoxide-olefin polymeric of claim 8, wherein d is about 0.01～about 7.0.
11. by the described carbon monoxide-olefin polymeric of claim 8, wherein catalyst comprises phosphorus.
12. by the described carbon monoxide-olefin polymeric of claim 8, wherein catalyst comprises at least a or its mixture in potassium, caesium, the sodium.
13. by the described carbon monoxide-olefin polymeric of claim 8, wherein carbon monoxide-olefin polymeric comprises the carrier that is selected from silica, aluminium oxide, zirconia, titanium oxide or its mixture.
14. by the described carbon monoxide-olefin polymeric of claim 13, wherein carrier is about 30wt%～70wt% of catalyst.
15. by the described carbon monoxide-olefin polymeric of claim 8, wherein carbon monoxide-olefin polymeric comprises that average micelle size is the silica of about 8nm～about 100nm.
16. one kind is selected from propylene, the alkene of isobutene or its mixture is separately converted to acrylonitrile, the method of methacrylonitrile and its mixture, described method is included in the catalyst that contains catalytic oxidation thing compound and exists down, alkene reacts with the gas and the ammonia that contain molecular oxygen in the HTHP gas phase, described catalyst comprises rubidium, cerium, chromium, iron, bismuth, at least a in molybdenum and evil or nickel and the cobalt, optional magnesium and the optional phosphorus that comprises of comprising, antimony, tellurium, sodium, lithium, potassium, caesium, thallium, boron, germanium, tungsten, a kind of in the calcium, the relative scale of these elements is represented with following general formula.
Rb
aCe
bCr
cMg
dA
eFe
fBi
gY
hMo
12O
x
Wherein, A is Ni or Ni and Co combination,
Y is at least a or its mixture in P, Sb, Te, Li, Na, K, Cs, Tl, B, Ge, W, Ca, Zn, the rare earth element,
A be about 0.01～about 1,
B be about 0.01～about 3,
C be about 0.01～about 2,
D is 0～7,
E be about 0.01～about 10,
F be about 0.01～about 4,
G be about 0.05～about 4,
H is 0～about 3,
The numerical value that x is determined for other element valence requirement,
Wherein, b+c＞g, and catalyst does not contain manganese, noble metal or vanadium substantially.
17. by the described carbon monoxide-olefin polymeric of claim 16, wherein b is less than c.
18. by the described carbon monoxide-olefin polymeric of claim 16, wherein d is about 0.01～about 7.0.
19. by the described carbon monoxide-olefin polymeric of claim 16, wherein h is 0.
20. by the described carbon monoxide-olefin polymeric of claim 16, wherein catalyst comprises phosphorus.
21. by the described carbon monoxide-olefin polymeric of claim 16, wherein catalyst comprises at least a or its mixture in potassium, caesium, the sodium.
22. by the described carbon monoxide-olefin polymeric of claim 16, wherein carbon monoxide-olefin polymeric comprises the carrier that is selected from silica, aluminium oxide, zirconia, titanium oxide or its mixture.
23. by the described carbon monoxide-olefin polymeric of claim 22, wherein carrier is about 30wt%～70wt% of catalyst.
24. by the described carbon monoxide-olefin polymeric of claim 16, wherein carbon monoxide-olefin polymeric comprises that average micelle size is the silica of about 8nm～about 100nm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US43016302P | 2002-12-02 | 2002-12-02 | |
| US60/430,163 | 2002-12-02 | ||
| US10/717,130 | 2003-11-18 |
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|---|---|
| CN1723083A true CN1723083A (en) | 2006-01-18 |
| CN100342969C CN100342969C (en) | 2007-10-17 |
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|---|---|---|---|
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Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN100342969C (en) |
| MY (1) | MY136504A (en) |
| TW (1) | TWI315216B (en) |
| ZA (1) | ZA200504280B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101534945B (en) * | 2006-10-26 | 2012-08-29 | 大野绿水株式会社 | Fluidized-bed catalyst for the production of acrylonitrile and process for the production of acrylonitrile |
| CN102892498A (en) * | 2010-03-23 | 2013-01-23 | 伊内奥斯美国公司 | Improved mixed metal oxide ammoxidation catalysts |
| CN102892496A (en) * | 2010-03-23 | 2013-01-23 | 伊内奥斯美国公司 | High efficiency ammoxidation process and mixed metal oxide catalysts |
| CN102892497A (en) * | 2010-03-23 | 2013-01-23 | 伊内奥斯美国公司 | Attrition resistant mixed metal oxide ammoxidation catalysts |
| CN102892499A (en) * | 2010-03-23 | 2013-01-23 | 伊内奥斯美国公司 | Process for preparing improved mixed metal oxide ammoxidation catalysts |
| CN101524645B (en) * | 2008-03-03 | 2013-04-10 | 大野绿水株式会社 | Catalyst for producing acrylonitrile and process for producing acrlyonitrile |
| CN104661745A (en) * | 2012-09-27 | 2015-05-27 | 旭化成化学株式会社 | Composite oxide catalyst, method for producing same, and method for producing unsaturated nitrile |
| CN107614102A (en) * | 2016-01-25 | 2018-01-19 | 旭化成株式会社 | The manufacture method of fluid bed ammoxidation reaction catalyst and acrylonitrile |
| CN113828324A (en) * | 2021-10-18 | 2021-12-24 | 黑龙江省君鑫化工有限公司 | Catalyst for acrylonitrile production |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5834394A (en) * | 1996-08-06 | 1998-11-10 | China-Petro-Chemical Corporation | Fluidized-bed catalyst for propylene ammoxidation to acrylonitrile |
| DE60030302T2 (en) * | 1999-10-18 | 2007-08-30 | Mitsubishi Rayon Co., Ltd. | A METHOD FOR THE PRODUCTION OF ACRYLNITRILE, A CATALYST FOR THIS AND A METHOD FOR THE PRODUCTION THEREOF |
| JP4159759B2 (en) * | 2001-04-13 | 2008-10-01 | ダイヤニトリックス株式会社 | Method for producing molybdenum-bismuth-iron-containing composite oxide fluidized bed catalyst |
-
2003
- 2003-11-19 CN CNB2003801048830A patent/CN100342969C/en not_active Expired - Lifetime
- 2003-11-24 TW TW092132906A patent/TWI315216B/en not_active IP Right Cessation
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101534945B (en) * | 2006-10-26 | 2012-08-29 | 大野绿水株式会社 | Fluidized-bed catalyst for the production of acrylonitrile and process for the production of acrylonitrile |
| CN101524645B (en) * | 2008-03-03 | 2013-04-10 | 大野绿水株式会社 | Catalyst for producing acrylonitrile and process for producing acrlyonitrile |
| CN102892497B (en) * | 2010-03-23 | 2014-12-31 | 伊内奥斯美国公司 | Attrition resistant mixed metal oxide ammoxidation catalysts |
| CN102892497A (en) * | 2010-03-23 | 2013-01-23 | 伊内奥斯美国公司 | Attrition resistant mixed metal oxide ammoxidation catalysts |
| CN102892499A (en) * | 2010-03-23 | 2013-01-23 | 伊内奥斯美国公司 | Process for preparing improved mixed metal oxide ammoxidation catalysts |
| CN102892496A (en) * | 2010-03-23 | 2013-01-23 | 伊内奥斯美国公司 | High efficiency ammoxidation process and mixed metal oxide catalysts |
| CN102892498A (en) * | 2010-03-23 | 2013-01-23 | 伊内奥斯美国公司 | Improved mixed metal oxide ammoxidation catalysts |
| CN102892499B (en) * | 2010-03-23 | 2015-01-28 | 伊内奥斯美国公司 | Process for preparing improved mixed metal oxide ammoxidation catalysts |
| CN102892498B (en) * | 2010-03-23 | 2015-03-25 | 伊内奥斯美国公司 | Improved mixed metal oxide ammoxidation catalysts |
| CN102892496B (en) * | 2010-03-23 | 2015-04-29 | 伊内奥斯美国公司 | High efficiency ammoxidation process and mixed metal oxide catalysts |
| CN104661745A (en) * | 2012-09-27 | 2015-05-27 | 旭化成化学株式会社 | Composite oxide catalyst, method for producing same, and method for producing unsaturated nitrile |
| CN107614102A (en) * | 2016-01-25 | 2018-01-19 | 旭化成株式会社 | The manufacture method of fluid bed ammoxidation reaction catalyst and acrylonitrile |
| CN110252324A (en) * | 2016-01-25 | 2019-09-20 | 旭化成株式会社 | The manufacturing method of fluidized bed ammoxidation reaction catalyst and acrylonitrile |
| CN113828324A (en) * | 2021-10-18 | 2021-12-24 | 黑龙江省君鑫化工有限公司 | Catalyst for acrylonitrile production |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200417408A (en) | 2004-09-16 |
| TWI315216B (en) | 2009-10-01 |
| ZA200504280B (en) | 2006-08-30 |
| MY136504A (en) | 2008-10-31 |
| CN100342969C (en) | 2007-10-17 |
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