CN102989469A - Multi-metal oxide catalyst and preparation method thereof - Google Patents
Multi-metal oxide catalyst and preparation method thereof Download PDFInfo
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- CN102989469A CN102989469A CN2011102650975A CN201110265097A CN102989469A CN 102989469 A CN102989469 A CN 102989469A CN 2011102650975 A CN2011102650975 A CN 2011102650975A CN 201110265097 A CN201110265097 A CN 201110265097A CN 102989469 A CN102989469 A CN 102989469A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 264
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims description 73
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 10
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 239000002002 slurry Substances 0.000 claims description 59
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 43
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052622 kaolinite Inorganic materials 0.000 claims description 22
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 229910052750 molybdenum Inorganic materials 0.000 claims description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 17
- 239000011733 molybdenum Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 11
- 238000000975 co-precipitation Methods 0.000 claims description 10
- 239000000470 constituent Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- -1 oxide Chemical compound 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 46
- 230000000694 effects Effects 0.000 abstract description 20
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229910052714 tellurium Inorganic materials 0.000 abstract description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009825 accumulation Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 97
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 17
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 16
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 16
- 239000000843 powder Substances 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 13
- 239000012018 catalyst precursor Substances 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 9
- 239000007921 spray Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000011247 coating layer Substances 0.000 description 7
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical class [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
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical class [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- PTFXACQNOUVLPN-UHFFFAOYSA-N O=CC(C)=C.C(C=C)(=O)O Chemical compound O=CC(C)=C.C(C=C)(=O)O PTFXACQNOUVLPN-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical class [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical class [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical class [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
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical class [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a multi-metal oxide catalyst, the composition of which is MoaBibFecCodSieAmBnOxSilicon is a carrier added in the catalyst, A is at least one element selected from nickel, tellurium, zirconium, vanadium and lanthanum; b is at least one element selected from alkali metals; o is oxygen; a. b, c, d, e, m, n represent the atomic ratio of each element, wherein a is a number of 12 to 14, b is a number of 2 to 10, c is a number of 1 to 8, d is a number of 1 to 8, e is a number of 1 to 60, m is a number of 0.1 to 3, n is a number of 0 to 3, and i is a number determined by the oxygen of each oxide. The catalyst can effectively reduce local heat accumulation of the single-tube reactor, inhibit the formation of hot spots, and has the characteristics of high reaction activity and selectivity and long service life.
Description
Technical field
The present invention relates to propylene or multi-metal-oxide catalyst of corresponding unsaturated aldehyde and preparation method thereof is produced in the selective isobutene oxidation.More specifically, relate to a kind of catalyst with double-deck poly-metal deoxide, be used for catalyzing propone oxidation acrolein or isobutylene oxidation isobutylaldehyde processed.
Background technology
It is strong exothermal reaction that the propylene gas phase catalytic oxidation reaction prepares methacrylaldehyde, moment is assembled a large amount of reaction heat in reactor, form hot localised points, if can not remove timely and effectively reaction heat, the heat that moment is gathered is constantly accumulated, will cause the catalyst activity component loss, come off, to such an extent as to catalyst activity reduction, the lost of life, and cause because over oxidation reacts the formation that aggravates accessory substance, thereby reduce methacrylaldehyde and acrylic acid yield.Even cause and runaway reaction make sintering of catalyst.
The appearance of " progress of oxidation acrylic acid synthesizing process and catalyst " (petrochemical industry, the 7th phase of the 39th volume in 2010) social focus also can make the catalyst damage evil, shortens the service life of catalyst.Take 80,000 ton/years of acroleic acid devices as example, propylene oxidation prepares and needs more than 25000 tubulation in the acrolein reaction device, and acrolein oxidation prepares also needs more than 25000 tubulation in the acrylic acid reactor, load altogether more than 100 ton of methacrylaldehyde, acrylic acid catalyst.More than 50,000 reaction tube, the filling of catalyst guarantee not fill empty certain difficulty that has, if because focus is crossed the very fast sintering of high catalyst, again change in a short time agent, it is huge can envisioning its economic loss again; In addition, carry out under cryogenic conditions as much as possible for methacrylaldehyde, acrylic acid production, because the reaction needed salt bath heating, its energy resource consumption of keeping production also is huge spending; Because the generation of focus is high temperature resistant to the requirement of reaction tube tubing, for up to ten thousand reaction tubes, the tubing expense is exactly a very large cost payout.Therefore, if the generation of establishment beds focus can bring huge economic benefit to large-scale industrial production.
At present, there is several different methods can reduce or avoid gathering and peroxidization of focus, as: Japanese patent laid-open 04-217932 has proposed a kind of method that suppresses the appearance of focus or the hot polymerization collection on the focus, namely by preparing multiple catalyst with different possessive volumes, and the mode from the unstripped gas inlet side to the minimizing of outlet one side catalyst possessive volume, fill successively reaction tube, but the possessive volume of catalyst is subjected to the restriction of reaction tube diameter, and it is also very difficult that multiple catalysts is filled into reaction tube.CN1210511A prepares the multiple catalyst-loaded catalyst layer that arranges with different activities in reaction tube, according to active uprise arranged sequentially above-mentioned several catalyst-loaded from the entrance of unstripped gas to outlet.The method that other is also arranged, for example inert substance and catalyst mix, reduce the activity of catalyst, be loaded into the reactor inlet place, Japan special permission disclose 10614/1972 to sneak into heat resistanceheat resistant point formation catalyst in catalyst is inert substance with catalyst dilution, and Japanese Patent Publication 36739/1987 is made catalyst the method for tubulose.The Catalyst packing that the unstrpped gas porch reduces with active component is arranged again.CN01111960.8 uses fixed bed shell and tube reactor, in the presence of catalyst, prepare methacrylaldehyde and acrylic acid by the propylene gas phase catalytic oxidation reaction, the method is the generation of focus or the hot polymerization collection on focus in the inhibitory reaction district effectively, this catalyst consist of Mo
aW
bBi
cFe
dA
eB
fC
gD
hE
iO
x, wherein the implication of Mo, W, Bi, Fe, A, B, C, D, E and O and a, b, c, d, e, f, g, h, i and x is as described in the specification.The feature of the method is the multiple catalysts that preparation has above-mentioned composition, but (α) temperature of possessive volume, (β) calcining and/or (γ) kind and/or the quantity of alkali metal is different, and press the mode of catalyst activity from the unstripped gas entrance to Increasing exports, catalyst is filled into reaction zone successively.CN00122609.6 provides under the condition that has the oxide catalyst that contains the Mo-Bi-Fe compound, produce methacrylaldehyde and acrylic acid by the vapor phase propylene oxide, described catalyst is filled in the multitubular reactor of fixed bed, and the method can generate methacrylaldehyde and acrylic acid with high stable yield in long-time.The method is characterized in that each distinguishes the filling different catalysts in each tubular reactor that disposes vertically two or more reaction zones, the ratio of namely filling out Bi the catalyst and/or Fe content and Mo content from the gas access end to gas outlet end reduces.CN1672790A provides a kind of catalyzing propone aldehyde gaseous oxidation system acrylic acid catalyst, described catalyst comprises molybdenum and vanadium, also comprise at least a volatile catalyst toxic component, its amount is 10 to 100ppb quality through ion chromatography measurement, this catalyst can reduce the temperature of hot spot, and suppresses the reduction of the reaction efficiency of thermal degradation.Specific practice is, comprises and originally has in the highly active catalyst by the volatility toxic component that makes specified quantitative, and catalytic activity descends momently, can reduce the temperature of hot spot.CN1165055A by catalytic active component is divided be loaded on the carrier after, calcine the generation that the catalyst of load sharing suppresses focus, the average grain diameter of catalyst is 4～16mm, the average grain diameter of carrier is 3～12mm, calcining heat is 500～600 ℃.CN1314331A provides the catalyst of a kind of Mo-W-Bi-Fe of containing, this catalyst by changing possessive volume calcining heat and/or alkali metal kind and/or quantity and according to catalyst activity from the inlet side of unstripped gas to the mode that outlet one side increases, fill successively reaction zone with described multiple types catalyst.Catalyst reaction tube axially on be divided at least two-layerly, this catalyst is the multiple types catalyst with different activities level, can be by changing calcining heat and/or wherein kind and/or the quantity of alkali metal obtain.The appearance of focus or the hot polymerization collection on the focus are by establishment.CN1472008A provides a kind of supported catalyst, and this catalyst carrier has multidimensional structure, with the self supporting type multidimensional carrier structure of preformed (such as foam, overall structure, fabric or other) or comprise Nb
2O
5, cordierite, partially stabilized zirconia, ceramic fibre or its mixture carrier, in succession described carrier deposition comprise any order at least one molybdenum-containing layer, at least one contains the vanadium layer, at least one contains the carbon monoxide-olefin polymeric that tellurium layer and at least one contain the X layer and forms the load carrier, after roasting supported catalyst.Be oxidized to unsaturated carboxylic acid for alkane and become unsaturated nitrile with ammoxidation of paraffins, enough conversion ratios are provided and are fit to selective.
All there is a problem in the method that above-mentioned inhibition focus produces, the catalyst that is filled in the reaction tube all has been diluted with various forms from the inlet to the outlet, active decline also can not change thinner ratio after both having made the catalyst runs some cycles, catalyst also can't provide higher activity again, not only loading, dismantle, separate, reclaim catalyst makes troubles, and can reduce the reactivity of catalyst, especially industrial long-term operation catalyst activity reduction is faster, affects catalyst life.In addition, under hot conditions, part active component molybdenum loses because of distillation from catalyst surface in the catalyst.Propylene, air and steam mixed airflow wash away the part loss of active component that also can make in the catalyst.For the loss that suppresses the molybdenum distillation causes active decay, CN1121504 can suppress dissipation effect and the over reduction of molybdenum composition by mixing copper component and zirconium and/or Titanium and/or Cerium with specified particle diameter and specific area; CN1445020 adds a small amount of tellurium and plays stable free molybdenum trioxide and the effect of molybdic acid copper crystal structure, and sublimation and the over reduction of molybdenum suppress to some extent; CN1583261 is take molybdenum, vanadium, copper, tungsten and/or niobium as key component, and the composite oxides or its hopcalite that consist of with other element form the loss that catalyst suppresses molybdenum.
Summary of the invention
The purpose of this invention is to provide a kind of propylene or multi-metal-oxide catalyst of corresponding unsaturated aldehyde and preparation method thereof is produced in the selective isobutene oxidation.Different from the method for above-mentioned reduction focus, there is gradient difference in catalyst granules of the present invention to exterior active combination of components substrate concentration internally, can effectively reduce fixed bed single tube reactor localized heat gathers, suppress emerging of focus, catalyst is easy-sintering not, and this catalyst has the characteristics of activity and selectivity height, good stability under high-speed spare.
The present invention relates to a kind of multi-metal-oxide catalyst, the chief component of this catalyst is represented by following general formula (I)
Mo
aBi
bFe
cCo
dSi
eA
mB
nO
x (I)
Wherein: Mo is molybdenum, and Bi is bismuth, and Fe is iron, and Co is cobalt, and Si is silicon, and silicon is the carrier that adds in the catalyst, and A is at least a element that is selected from nickel, titanium, zirconium, vanadium, the lanthanum; B is at least a element that is selected from the alkali metal; O is oxygen; A, b, c, d, e, m, n represent respectively each element atomic ratio, and wherein a is a number of 12～14, and b is a number of 2～10, preferred 2～6; C is a number of 1～8, preferred 1～5; D is a number of 1～8, preferred 1～5; E is a number of 0.5～60, m is a number of 0.05～3, n is a number of 0～3, i is the numerical value by the oxygen decision of each oxide, described multi-metal-oxide catalyst has interior outer double-layer structure, every layer of catalyst chief component is identical, but the total content of one or more in silica, aluminium oxide or the carborundum is different, the total content of one or more in outer silica, aluminium oxide or the carborundum is than the height of internal layer parent, in molar content, each constituent content concentration ratio internal layer parent of catalyst outer layer is low.
Catalyst of the present invention is double-decker, there is gradient difference in catalyst to exterior active combination of components substrate concentration internally, mainly be achieved concentration difference by add the materials such as different amount silica, aluminium oxide, carborundum at ectonexine, that is to say, the total content of one or more in outer silica, aluminium oxide or the carborundum is higher than internal layer parent, in molar content, outer each constituent content is than this constituent content of internal layer parent low 0.5～30%, preferred 1～15%.Catalyst inner layer of the present invention also can not add silicon.
The present invention can add active component lanthanum or titanium, lanthanum and cobalt, nickel etc. can both form stable crystal phase structure, the good dispersion of molybdenum, thereby suppressing part active component molybdenum loses because of distillation from catalyst surface, the active component molybdenum is difficult for running off, active component molybdenum content is substantially constant before and after the catalyst reaction, delays active deterioration rate, catalyst activity and good stability.Lanthanum and molybdenum, cobalt ratio are suitable, and A is lanthanum in the general formula (I), and m is a number of 0.05～2, and n is a number of 0.1～2, and too much the affiliation that adds of lanthanum is competed molybdenum with bismuth and cobalt, affects catalyst activity.
Multi-metal-oxide catalyst of the present invention adopts common preparation method to get final product, as adopting following step preparation.
At first, Kaolinite Preparation of Catalyst internal layer parent:
To contain Mo, A among the Bi, the compound of Fe, Co, Si and general formula (I)
mB
nEach the elemental constituent compound that relates to dissolving and mix, carry out forming internal layer parent slurries after the co-precipitation, oven dry, moulding, roasting get the catalyst inner layer parent;
Secondly, method according to Kaolinite Preparation of Catalyst internal layer parent slurries prepares the outer layer catalyst slurries, add in silica, aluminium oxide or the carborundum one or more in the outer layer catalyst slurries preparation process, so that each concentration of element is lower than the concentration of this element of adjacent inner layer in the outer layer catalyst slurries;
At last, the outer layer catalyst for preparing is coated on the catalyst inner layer parent successively, after roasting, gets finished catalyst.
Catalyst inner layer parent of the present invention is after the moulding and outer all need to compare not the respectively catalyst of roasting at 300～580 ℃ of lower roasting 3～10h after coating, and repeatedly roasting can improve the active and stable of catalyst.Can be that open roasting also can be enclosed roasting, calcination atmosphere can be the inert gases such as helium, nitrogen, argon gas.
Catalyst layer chaps during thick roasting very much easily, for fear of be full of cracks be preferably in apply after 55～125 ℃ of oven dry, and then roasting.The outer layer catalyst bed thickness that is coated on the internal layer parent is 1.0～2.5mm, preferred 1.5～2mm.
The compound of each component of catalyst of the present invention can use nitrate, ammonium salt, sulfate, oxide, hydroxide, chloride, acetate of each element etc.Active component is not all used nitrate as far as possible, the oxide contaminant atmosphere that when roasting, produces, and be not easy moulding, manufacturing schedule is slow, but nitrate is easy to dissolving, and nitrate preferably uses with other forms of compound, be easy to moulding, speed production efficient.
After the catalyst inner layer parent slurries of the present invention oven dry, the preferred forming methods such as extrusion molding, granulating and forming, compression molding that adopt are processed into spherical, hollow spheres, ellipticity, cylindric, hollow circuit cylinder etc., preferably hollow circuit cylinder or spherical usually.
Preferably use binding agent when catalyst of the present invention applies, make ectonexine catalyst bonding more firm.Be under the rolling condition at the internal layer parent and spray binding agent and infiltrate the surface, the outer layer catalyst powder for preparing of spraying more also can be put into the internal layer parent outer layer catalyst slurries that the prepare coating of rolling.Binding agent is selected from one or more in water, alcohols or the ethers.Alcohols such as ethanol, propyl alcohol, butanols; Ethers such as ether and butyl ether.
Each of catalyst of the present invention layer surface be uneven, rough surface preferably, is conducive to apply, and bonding is more firm between layers.
Intensity, the efflorescence degree of the present invention in order to improve catalyst can add in glass fibre, graphite, pottery or the various whisker one or more in above-mentioned outer layer catalyst.
The present invention has double-decker, and internal layer also can be called the internal layer parent.
Because catalyst initial reaction activity is very high, so be easy to produce focus or produce heat localization at fixed bed single tube reactor bed, catalyst is easy to sintering, and this loses concerning suitability for industrialized production methacrylaldehyde acrylic acid is very serious.Pass into a certain amount of steam in the raw material, because specific heat of water is large, can take away a large amount of reaction heat, make active decline but the steam input greatly often makes catalyst member active component solution-off.The present invention has double-deck multi-metal-oxide catalyst by preparation, make catalyst granules have gradient difference to exterior active combination of components substrate concentration internally, catalyst outer layer active component concentration is lower than internal layer active component concentration, like this, under the high-speed reaction condition, because the active component concentration of catalyst outer surface is low, so corresponding activity is also low, therefore can emerging of establishment focus and gathering of heat, reduce the growing amount of accessory substance (such as hydrocarbon), improve the selective of purpose product.This has double-deck catalyst and has good water repelling property.And when catalyst runs after a period of time, catalyst has release effects, wash away lower at the mixed airflow long period, even the catalyst surface active component has part to run off, but because internal layer catalyst active component concentration is higher, can play additional effect, so can keep the catalyst activity lasting stability.
The evaluating catalyst performance indications are defined as follows:
The molal quantity of propylene * 100% in the total mole number/raw material of propylene conversion (%)=propylene reaction
Selective (the %)=propylene of methacrylaldehyde is converted into the total mole number of the molal quantity of methacrylaldehyde/propylene reaction * 100%
The specific embodiment
The below has double-deck multi-metal-oxide catalyst and preparation method thereof with specific embodiment explanation, and this catalyst prepares the catalytic performance of methacrylaldehyde in the Propylene Selectivity oxidation, but scope of the present invention is not limited to these embodiment.The propylene that following examples adopt is the high concentration propylene of propylene content 〉=99.6% (volume fraction).
Embodiment 1:
The preparation of catalyst 1
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active component slurries (a)
Under stirring condition, get 160 gram ammonium molybdates and be dissolved in (water temperature is more than 65 ℃) in the 500ml pure water, obtain slurries (1), then get 85.6 the gram cobalt nitrates, 7 the gram potassium nitrate, 84.8 the gram ferric nitrates, 0.6 the gram titanium dioxide be dissolved in (water temperature is more than 65 ℃) in the 500ml pure water, fully mix, obtain slurries (2).Get again 237.7 gram bismuth nitrates, under stirring condition, be dissolved in rare nitric acid, obtain slurries (3).Then, slurries (1) mix with slurries (2), obtain slurries (4), then slurries (3) are added in the slurries (4), obtain active component slurries (a).
(2) preparation of catalyst inner layer parent
In active component slurries (a), add 8 gram silica, 80 ℃ of strong stirrings carried out heat drying behind the coprecipitation reaction in 2 hours, in nitrogen with 160 ℃ of heat treatments 3 hours, then be a granulated into the ball shape that diameter is 2mm through banded extruder extruding, rolling, dry rear 450 ℃ of roastings 4 hours for 45 ℃, make catalyst Precursors, this catalyst inner layer parent consists of: Mo
13Bi
7Fe
3Co
42K
1Ti
01Si
19
Step 2: Kaolinite Preparation of Catalyst is outer
(1) preparation of active component slurries (a)
Preparation with active component slurries (a) in the embodiment 1 catalyst inner layer parent is identical.
(2) preparation of catalyst outer layer
Active component slurries (a) and 24 gram silicon dioxide powders are carried out coprecipitation reaction heat drying after 40 minutes, and with 150 ℃ of heat treatments 3 hours, then 500 ℃ of roastings were 4 hours in nitrogen, processed to get the catalyst outer layer powder through pulverizing, grind, sieving.
Step 3: Kaolinite Preparation of Catalyst 1
The catalyst inner layer parent of step 1 preparation is placed round bottom container, under container rotation condition, spray ethanolic solution to catalyst Precursors, under the condition of abundant wetting catalyst inner layer parent, stop operating, put it into rapidly in the round bottom container of the outer layer catalyst powder that is placed with step 2 gained of another rotation, apply, coating layer thickness is at 1.0～2.0mm, and 75 ℃ of oven dry of gained catalyst namely got catalyst 1 in 4 hours by 450 ℃ of roastings.
Comparative Examples 1:
Take the internal layer parent of catalyst 1 as comparative catalyst 1, make the ball that diameter is 4mm, reaction condition is with the appreciation condition of catalyst 1.
Comparative Examples 2:
Take the skin of catalyst 1 as comparative catalyst 2, make the ball that diameter is 4mm, reaction condition is with the appreciation condition of catalyst 1.
Embodiment 2:
The preparation of catalyst 2
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active component slurries (a)
Under stirring condition, get 173 gram ammonium molybdates and be dissolved in (water temperature is more than 65 ℃) in the 500ml pure water, obtain slurries (1), then get 69 the gram cobalt nitrates, 40.7 the gram nickel nitrates, 16.8 the gram magnesium nitrates, 183.8 the gram ferric nitrates be dissolved in (water temperature is more than 65 ℃) in the 500ml pure water, fully mix, obtain slurries (2).Get again 169.8 gram bismuth nitrates, under stirring condition, be dissolved in rare nitric acid, obtain slurries (3).Then, slurries (1) mix with slurries (2), obtain slurries (4), then slurries (3) are added in the slurries (4), obtain active component slurries (a).
(2) preparation of catalyst Precursors
In slurries (a), add 12.6 gram silica, 80 ℃ of strong stirrings carried out heat drying behind the coprecipitation reaction in 2 hours, in nitrogen with 160 ℃ of heat treatments 5 hours, then be the hollow columnar particle of φ 4.5 * 5mm through the banded extruder extrusion modling, dry rear 450 ℃ of roastings 4 hours for 125 ℃, make catalyst Precursors, this catalyst Precursors consists of: Mo
14Bi
5Fe
65Co
34Ni
23Mg
13
Step 2: Kaolinite Preparation of Catalyst is outer
(1) preparation of active component slurries (a)
Preparation with active component slurries (a) in the embodiment 2 catalyst inner layer parents is identical.
(2) preparation of catalyst outer layer
Active component slurries (a) and 36 gram silicon dioxide powders are carried out answering after the co-precipitation heat drying after 50 minutes, and with 160 ℃ of heat treatments 3 hours, then 500 ℃ of roastings were 4 hours in nitrogen, processed to get the catalyst outer layer powder through pulverizing, grind, sieving.
Step 3: Kaolinite Preparation of Catalyst 2
The catalyst inner layer parent of step 1 preparation is placed round bottom container, under container rotation condition, spray ethanolic solution to catalyst Precursors, abundant wetting catalyst inner layer parent, put it into rapidly in the round bottom container of the catalyst outer layer that is placed with step 2 gained of another rotation, apply, coating layer thickness is when 0.8～1.0mm, taking-up internal layer parent is put into another round bottom container rotation and is sprayed ethanolic solution after one to two minute again, then putting into the round bottom container that catalyst outer layer is housed continues to apply, until coating layer thickness stops to apply when 1.5～2.0mm, 105 ℃ of oven dry of gained catalyst namely got catalyst 2 in 3 hours by 500 ℃ of roastings.
Comparative Examples 3:
Take the internal layer parent of catalyst 2 as comparative catalyst 3, the banded extruder extrusion modling is the hollow columnar particle of φ 5 * 5mm, and reaction condition is with the appreciation condition of catalyst 1.
Comparative Examples 4:
Take the skin of catalyst 2 as comparative catalyst 4, the banded extruder extrusion modling is the hollow columnar particle of φ 5 * 5mm, and reaction condition is with the appreciation condition of catalyst 1.
Embodiment 3:
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active component slurries (a)
The preparation method of active component slurries (a) and raw materials used (following examples are identical) just add 4.2 gram potassium nitrate, 8.2 gram ammonium metavanadates with embodiment 1.
(2) preparation of catalyst inner layer parent
In slurries (a), add 5.6 gram silica, 80 ℃ of strong stirrings carried out heat drying behind the coprecipitation reaction in 3 hours, in nitrogen with 160 ℃ of heat treatments 3 hours, then be the hollow columnar particle of φ 4.5 * 5mm through the banded extruder extrusion modling, dry rear 450 ℃ of roastings 4 hours for 85 ℃, make catalyst Precursors, this catalyst inner layer parent consists of: Mo
13Bi
3Fe
4Co
24V
1K
06
Step 2: Kaolinite Preparation of Catalyst is outer
(1) preparation of active component slurries (a)
Preparation and raw materials used identical (following examples are identical) with active component slurries (a) in the embodiment 3 catalyst inner layer parents.
(2) preparation of catalyst outer layer
Active component slurries (a) and 18.8 gram silicon dioxide powders are carried out answering after the co-precipitation heat drying after 50 minutes, and with 160 ℃ of heat treatments 3 hours, then 500 ℃ of roastings were 4 hours in nitrogen, processed to get the catalyst outer layer powder through pulverizing, grind, sieving.
Step 3: Kaolinite Preparation of Catalyst 3
The catalyst inner layer parent of step 1 preparation is placed round bottom container, under container rotation condition, spray diethyl ether solution to catalyst Precursors, under the condition of abundant wetting catalyst inner layer parent, stop operating, put it into rapidly in the round bottom container of the catalyst outer layer that is placed with step 2 gained of another rotation, apply, coating layer thickness is at 1.0～2.0mm, and 90 ℃ of oven dry of gained catalyst namely got catalyst 3 in 3 hours by 550 ℃ of roastings.
Comparative Examples 5:
Take the internal layer parent of catalyst 3 as comparative catalyst 5, be the hollow columnar particle of φ 5 * 5mm through the banded extruder extrusion modling then, reaction condition is with the appreciation condition of catalyst 1.
Comparative Examples 6:
Take the skin of catalyst 3 as comparative catalyst 6, be the hollow columnar particle of φ 5 * 5mm through the banded extruder extrusion modling then, reaction condition is with the appreciation condition of catalyst 1.
Embodiment 4:
Step 1: Kaolinite Preparation of Catalyst internal layer parent
With preparation method and raw materials used identical (following examples are identical) of embodiment 2 catalyst inner layer parents, just add 6.5 gram magnesium nitrates, 16.4 gram cesium nitrates, 11.4 gram silica, this catalyst inner layer parent consists of: Mo
12Bi
8Fe
15Co
5Mg
05Cs
12
Step 2: Kaolinite Preparation of Catalyst is outer
With preparation method and raw materials used identical (following examples are identical) of embodiment 2 catalyst outer layer, just add 52.4 gram silica and 10.2 gram carborundum.
Step 3: Kaolinite Preparation of Catalyst 4
The catalyst inner layer parent of step 1 preparation is placed round bottom container, under container rotation condition, spray ethanolic solution to catalyst, under the condition of abundant wetting catalyst inner layer parent, spray the outer layer catalyst powder of step 2 gained, apply, coating layer thickness is at 0.8～1.5mm, and 50 ℃ of oven dry of gained catalyst got catalyst 4 in 5 hours by 400 ℃ of roastings.
Comparative Examples 7:
Take the outer layer catalyst of catalyst 4 as comparative catalyst 7, be the hollow columnar particle of φ 5 * 5mm through the banded extruder extrusion modling, reaction condition is with the appreciation condition of catalyst 1.
Embodiment 5:
Step 1: Kaolinite Preparation of Catalyst internal layer parent
With the preparation method of embodiment 2 catalyst outer layer and raw materials used identical, add 7 gram potassium nitrate, 28.5 gram zirconium nitrates, 6.8 gram lanthanum nitrates, 10.3 gram silica and 5.6 gram aluminium oxide, this catalyst inner layer parent consists of: Mo
12Bi
9Fe
8Co
1K
1Zr
12La
03
Step 2: Kaolinite Preparation of Catalyst is outer
Preparation with embodiment 2 catalyst outer layer is identical, just adds 25.2 gram silica and 14.8 gram aluminium oxide.
Step 3: Kaolinite Preparation of Catalyst 5
The catalyst inner layer parent of step 1 preparation is placed round bottom container, under container rotation condition, spray distilled water to catalyst Precursors, under the condition of abundant wetting catalyst inner layer parent, spray the outer layer catalyst powder of step 2 gained, apply, coating layer thickness is at 0.8～1.2mm, and 45 ℃ of oven dry of gained catalyst got catalyst 5 in 6 hours by 500 ℃ of roastings.
Comparative Examples 8:
Take the internal layer catalyst of catalyst 5 as comparative catalyst 8, but do not contain lanthanum, catalyst consists of Mo
12Bi
9Fe
8Co
1K
1Zr
12Reaction condition is with the appreciation condition of catalyst 1.
Embodiment 6:
With the preparation method of embodiment 5 catalyst and raw materials used identical, internal layer adds 10 gram silica, outer 8.6 gram carborundum and the 13.5 gram silica of adding, and the catalyst inner layer parent consists of: Mo
12Bi
5Fe
2Co
25K
1Zr
01La
11
Embodiment 7:
The preparation of catalyst 7
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active component slurries (a)
Under stirring condition, get 148 gram ammonium molybdates and be dissolved in (water temperature is more than 65 ℃) in the 500ml pure water, obtain slurries (1), then get 61 the gram cobalt nitrates, 42.4 the gram ferric nitrates be dissolved in (water temperature is more than 65 ℃) in the 500ml pure water, fully mix, obtain slurries (2).Get again 135.8 gram bismuth nitrates, under stirring condition, be dissolved in rare nitric acid, obtain slurries (3).Then, slurries (1) mix with slurries (2), obtain slurries (4), then slurries (3) are added in the slurries (4), obtain active component slurries (a).
(2) preparation of catalyst inner layer parent
In active component slurries (a), add 5.6 gram silica, 80 ℃ of strong stirrings carried out heat drying behind the coprecipitation reaction in 2 hours, in nitrogen with 160 ℃ of heat treatments 3 hours, then be a granulated into the ball shape that diameter is 2mm through banded extruder extruding, rolling, dry rear 450 ℃ of roastings 3.5 hours for 60 ℃, make catalyst Precursors, this catalyst inner layer parent consists of: Mo
12Bi
4Fe
15Co
3
Step 2: Kaolinite Preparation of Catalyst is outer
(1) preparation of active component slurries (a)
Preparation with active component slurries (a) in the embodiment 1 catalyst inner layer parent is identical.
(2) preparation of catalyst outer layer
Active component slurries (a) and 3.3 gram silicon dioxide powders and 3.4 gram graphite powders are carried out coprecipitation reaction heat drying after 40 minutes, in nitrogen with 150 ℃ of heat treatments 4 hours, then 460 ℃ of roastings are 4 hours, process to get the catalyst outer layer powder through pulverizing, grind, sieving.
Step 3: Kaolinite Preparation of Catalyst 7
The catalyst inner layer parent of step 1 preparation is placed round bottom container, under container rotation condition, spray ethanolic solution to catalyst Precursors, under the condition of abundant wetting catalyst inner layer parent, stop operating, put it into rapidly in the round bottom container of the outer layer catalyst powder that is placed with step 2 gained of another rotation, apply, coating layer thickness is at 1.0～2.0mm, and 105 ℃ of oven dry of gained catalyst namely got catalyst 7 in 6 hours by 350 ℃ of roastings.
Oxidation reaction
Fixed bed single tube reactor internal diameter 25mm, in establish thermocouple, the reactor above-mentioned catalyst of 35ml of packing into, salt bath heating.From above-mentioned reaction tube porch with air speed 850h
-1Import the mist of propylene 10 volume %, air 73 volume %, steam 17 volume %.The performance of catalyst as shown in Table 1 and Table 2.Reacted 20 hours and 800 hours, catalyst establishment focus, the difficult losses such as catalyst activity component molybdenum, catalyst catalytic performance is stable.Comparative Examples 1～8 catalyst can not the establishment focus, and poor selectivity reacts behind 800 hours rear catalysts that activity obviously descends under the washing away of the mixed airflows such as steam.
20 hours post-evaluation results of table 1 reaction
800 hours post-evaluation results of table 2 reaction
Claims (13)
1. multi-metal-oxide catalyst is characterized in that the catalyst chief component is shown in general formula (I):
Mo
aBi
bFe
cCo
dSi
eA
mB
nO
x (I)
Wherein: Mo is molybdenum, and Bi is bismuth, and Fe is iron, and Co is cobalt, and Si is silicon, and silicon is the carrier that adds in the catalyst, and A is at least a element that is selected from nickel, titanium, zirconium, vanadium, the lanthanum; B is at least a element that is selected from the alkali metal; O is oxygen; A, b, c, d, e, m, n represents respectively each element atomic ratio, wherein a is a number of 12～14, b is a number of 2～10, c is a number of 1～8, d is a number of 1～8, e is a number of 0.5～60, m is a number of 0.1～3, n is a number of 0～3, i is that described multi-metal-oxide catalyst has interior outer double-layer structure, outer silica by the numerical value of the oxygen decision of each oxide, the total content of one or more in aluminium oxide or the carborundum is than the height of internal layer parent, in molar content, each constituent content concentration ratio internal layer parent of catalyst outer layer is low.
2. catalyst according to claim 1 is characterized in that b is a number of 2～6.
3. catalyst according to claim 1 is characterized in that c is a number of 1～5.
4. catalyst according to claim 1 is characterized in that d is a number of 1～5.
5. catalyst according to claim 1 is characterized in that in molar content, and outer each constituent content is than this constituent content of adjacent inner layer low 0.5～30%.
6. catalyst according to claim 1 is characterized in that each constituent content of catalyst outer layer is than this constituent content of adjacent inner layer low 1～15%.
7. catalyst according to claim 1 is characterized in that A is selected from lanthanum or titanium, and m is a number of 0.05～2, and n is a number of 0.1～2.
8. the preparation method of each described catalyst is characterized in that comprising the steps: according to claim 1～7
At first, Kaolinite Preparation of Catalyst internal layer parent:
To contain Mo, A among the Bi, the compound of Fe, Co, Si and general formula (I)
mB
nEach the elemental constituent compound that relates to dissolving and mix, carry out forming internal layer parent slurries after the co-precipitation, oven dry, moulding, roasting get the catalyst inner layer parent;
Secondly, prepare the outer layer catalyst slurries according to the method for Kaolinite Preparation of Catalyst internal layer parent slurries, add in silica, aluminium oxide or the carborundum one or more in the outer layer catalyst slurries preparation process;
At last, the outer layer catalyst for preparing is coated on the catalyst inner layer parent successively, after roasting, gets finished catalyst.
9. the preparation method of described catalyst according to claim 8, it is characterized in that the internal layer parent after the moulding and outer after coating at 300～580 ℃ of lower roasting 3～10h, adopt open roasting or enclosed roasting, calcination atmosphere is helium, nitrogen or argon gas.
10. the preparation method of catalyst according to claim 8, a kind of in nitrate, ammonium salt, sulfate, oxide, hydroxide, chloride or the acetate of each element of the compound that it is characterized in that described each component.
11. the preparation method of catalyst according to claim 8 is characterized in that using binding agent when described catalyst applies, binding agent is selected from one or more in water, Ludox or the aluminium colloidal sol.
12. the preparation method of catalyst according to claim 8 is characterized in that using binding agent when described catalyst applies, binding agent is selected from one or more in alcohols or the ethers.
13. each described catalyst according to claim 1～7 is characterized in that adding one or more of glass fibre, graphite or pottery in each layer catalyst.
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| CN103638940A (en) * | 2013-11-08 | 2014-03-19 | 王善良 | Catalyst for synthesizing m-phenylenediamine from m-dinitrobenzene by hydrogenation reaction and application thereof |
| CN104649892A (en) * | 2013-11-19 | 2015-05-27 | 中国石油天然气股份有限公司 | Method for selectively oxidizing unsaturated aldehyde |
| CN104646016B (en) * | 2013-11-19 | 2017-06-06 | 中国石油天然气股份有限公司 | Unsaturated aldehyde oxidation catalyst and preparation method thereof |
| CN108855126A (en) * | 2017-05-11 | 2018-11-23 | 中国石油化工股份有限公司 | A kind of shell core formula catalyst and preparation method synthesizing m-phenylene diamine (MPD) |
| CN113522301A (en) * | 2021-06-28 | 2021-10-22 | 谷育英 | Catalyst for preparing unsaturated aldehyde by olefin oxidation and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103638940A (en) * | 2013-11-08 | 2014-03-19 | 王善良 | Catalyst for synthesizing m-phenylenediamine from m-dinitrobenzene by hydrogenation reaction and application thereof |
| CN104649892A (en) * | 2013-11-19 | 2015-05-27 | 中国石油天然气股份有限公司 | Method for selectively oxidizing unsaturated aldehyde |
| CN104646016B (en) * | 2013-11-19 | 2017-06-06 | 中国石油天然气股份有限公司 | Unsaturated aldehyde oxidation catalyst and preparation method thereof |
| CN108855126A (en) * | 2017-05-11 | 2018-11-23 | 中国石油化工股份有限公司 | A kind of shell core formula catalyst and preparation method synthesizing m-phenylene diamine (MPD) |
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| CN113522301A (en) * | 2021-06-28 | 2021-10-22 | 谷育英 | Catalyst for preparing unsaturated aldehyde by olefin oxidation and preparation method and application thereof |
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