CN104646015B - Propylene oxidation catalyst and preparation method thereof - Google Patents
Propylene oxidation catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN104646015B CN104646015B CN201310581371.9A CN201310581371A CN104646015B CN 104646015 B CN104646015 B CN 104646015B CN 201310581371 A CN201310581371 A CN 201310581371A CN 104646015 B CN104646015 B CN 104646015B
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- China
- Prior art keywords
- catalyst
- roasting
- oxide
- formula
- molybdenum
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- 239000003054 catalyst Substances 0.000 title claims abstract description 191
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims description 29
- 230000003647 oxidation Effects 0.000 title claims description 28
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims description 28
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims description 28
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 51
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000011733 molybdenum Substances 0.000 claims abstract description 43
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 22
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 11
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010937 tungsten Substances 0.000 claims abstract description 11
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011591 potassium Substances 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 32
- 229910052746 lanthanum Inorganic materials 0.000 claims description 17
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 17
- 229910052712 strontium Inorganic materials 0.000 claims description 16
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 16
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 13
- 239000006104 solid solution Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 238000000975 co-precipitation Methods 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910016300 BiOx Inorganic materials 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 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
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 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 description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 41
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 9
- 150000001336 alkenes Chemical class 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 abstract 1
- 230000007704 transition Effects 0.000 abstract 1
- 239000010949 copper Chemical group 0.000 description 37
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 35
- 239000012071 phase Substances 0.000 description 28
- 239000002131 composite material Substances 0.000 description 24
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 23
- 229910052802 copper Inorganic materials 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 239000007789 gas Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 16
- 229910052720 vanadium Inorganic materials 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000010955 niobium Substances 0.000 description 11
- 239000003377 acid catalyst Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052787 antimony Inorganic materials 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 229910052758 niobium Inorganic materials 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 229910052684 Cerium Inorganic materials 0.000 description 7
- 229910052785 arsenic Inorganic materials 0.000 description 7
- IKUPISAYGBGQDT-UHFFFAOYSA-N copper;dioxido(dioxo)molybdenum Chemical compound [Cu+2].[O-][Mo]([O-])(=O)=O IKUPISAYGBGQDT-UHFFFAOYSA-N 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910015667 MoO4 Inorganic materials 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910052715 tantalum Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910018864 CoMoO4 Inorganic materials 0.000 description 5
- 229910017354 Fe2(MoO4)3 Inorganic materials 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 230000002779 inactivation Effects 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229910002900 Bi2MoO6 Inorganic materials 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052792 caesium Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 229910052732 germanium Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910052701 rubidium Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- 229910005809 NiMoO4 Inorganic materials 0.000 description 3
- 229910002367 SrTiO Inorganic materials 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- NXGASACSZHOEHS-UHFFFAOYSA-N cerium lanthanum zirconium Chemical compound [Zr].[La].[Ce] NXGASACSZHOEHS-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 150000002927 oxygen compounds Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229910015142 FeMoO4 Inorganic materials 0.000 description 2
- 229930194542 Keto Natural products 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910002370 SrTiO3 Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001342 alkaline earth metals Chemical group 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000001427 coherent effect Effects 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 125000000468 ketone group Chemical group 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical compound [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000009418 renovation Methods 0.000 description 2
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- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 1
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 1
- 229910016525 CuMo Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- 229910017010 Fe2 (MoO4)3 Inorganic materials 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- JSYPCNDPJZERAR-UHFFFAOYSA-H antimony(3+) hexaacetate Chemical compound [Sb+3].C(C)(=O)[O-].[Sb+3].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] JSYPCNDPJZERAR-UHFFFAOYSA-H 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- MGLUJXPJRXTKJM-UHFFFAOYSA-L bismuth subcarbonate Chemical compound O=[Bi]OC(=O)O[Bi]=O MGLUJXPJRXTKJM-UHFFFAOYSA-L 0.000 description 1
- 229940036358 bismuth subcarbonate Drugs 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical class [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical group [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 239000011964 heteropoly acid 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
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- -1 oxo metal compound Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- ORSLXQZSKCIHDH-UHFFFAOYSA-N prop-2-enal;prop-2-enoic acid Chemical compound C=CC=O.OC(=O)C=C ORSLXQZSKCIHDH-UHFFFAOYSA-N 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a multi-metal oxide catalyst, which contains molybdenum, bismuth, iron, cobalt, tungsten and potassium elements, and also contains strontium titanate. The catalyst is used for olefin selective oxidation reaction, and has the characteristics of difficult loss of an active component molybdenum, difficult phase transition of an active phase, high reaction activity and selectivity and long service life.
Description
Technical field
The present invention relates to a kind of Propylene Selectivity oxidation produces multi-metal-oxide catalyst and its preparation side of acrylic aldehyde
Method.
Background technology
Aldehyde is prepared in industrial propylene oxidation, the reaction unit of acid is mainly many reaction tubes, is ensureing that catalyst is not burnt
On the premise of knot, long service life, improve selectivity and purpose product yield as far as possible, save the raw materials such as propylene, if raw material turns
Even if rate, acrylic aldehyde, acrylic acid yield improve 0.1～0.5 percentage point, the amount of the product obtaining is with hundreds of～thousands of tons of
Level increases, and its economic benefit is also very considerable.
It is mainly molybdenum system multicomponent catalyst with regard to propylene fraction oxidation acrolein, acrylic acid catalyst.Due to propylene
It is strong exothermal reaction that selective oxidation prepares the acrylic acid reaction of acrylic aldehyde, so be passed through the big water of specific heat in course of reaction steaming
Gas, effectively to remove reaction heat, but the easy loss under the washing away of the air-flows such as vapor such as active component molybdenum in catalyst.
And, under the high temperature conditions, in catalyst, part active component molybdenum loses because of distillation from catalyst surface.Active component molybdenum
Run off and lead to reduce activity, selectivity, intensity and the service life of catalyst, and molybdenum, in the deposition in response system downstream, hinders
Plug pipeline affects the long-term operation of system.
In addition, active component molybdenum in catalyst etc. enables keeping not running off, substantially change before and after the reaction of molybdenum equal size
Less, but easily there is phase in version through long-term operation activity compatible.Key component in catalyst includes Fe2(MoO4)3、
α-Bi2(MoO4)3、CoMoO4And NiMoO4, wherein α-Bi2(MoO4)3It is Active sites, play selective oxidation effect；Fe2
(MoO4)3Play redox facilitation；CoMoO4And NiMoO4Play Stability Analysis of Structures effect.However, the coprecipitation method system of adopting
Standby catalyst is many due to component, and process is complicated, and catalyst stabilization differs, although initial activity is very high, inactivation is fast.Lead to many
Component Mo-Bi-Co-Fe-O catalyst and Mo-V-O catalyst inactivation and stability decline factor have a lot, including because
The locally sublimation of Mo component caused by abnormal high temperature (focus) and the change of irreversible crystalline phase etc..These factors all can be drawn
Play the change of specificity of catalyst, lead to the service life reducing and shortening catalyst of catalyst activity.By urging to inactivation
Agent carries out phenetic analysis, finds Fe2(MoO4)3It is reduced into FeMoO4, and α-Bi2(MoO4)3It is changed into γ-Bi2MoO6.
Solve the above problems, the patent being related to is relatively more, for example, for suppressing the loss of molybdenum, CN1583261 is open a kind of
It is selectively oxidized the composition metal of reaction for the gas containing unsaturated aldehyde and a kind of gas of molecule-containing keto in the gas phase
Oxide catalyst, its catalyst consists of：[MoaVbCucXd]lYm[SbeZ1 fZ2 g]nOxWherein Mo is molybdenum, and V is vanadium, and Cu is copper,
Sb is antimony, and X is a kind of element being at least selected from tungsten and niobium, and Y is at least to be selected from titanium, a kind of element of antimony, Z1It is at least chosen from Fe
With a kind of element of nickel, Z2It is at least to be selected from silicon, aluminum, a kind of element of alkali and alkaline earth metal ions, a, b, c, d, e, f, g and x
Represent the atomic ratio number of its element, when on the basis of a=12, b is 1 to 6 number, and c is 0.5 to 4 number, and d is 0.05
To 4 number, e is 0.1 to 30 number, and f is 0 to 25 number, and g is 0.01 to 20 number；X is by meeting
A number needed for each metallic element combined oxidation state；Catalyst is made up of its each element oxide or composite oxides.
In order to improve the stability of catalyst, CN1130172 discloses a kind of acrylic acid catalyst, respectively use ammonium metavanadate and
Copper nitrate, and replace ammonium metavanadate with low price barium oxide and/or low price Cu oxide part and/or copper nitrate make vanadium metal and
Catalyst obtained by the raw material of copper or in addition to above-mentioned raw materials, is obtained using low price sb oxide and/or low price tin-oxide
Catalyst show there is a strengthened peak (vanadium-molybdenum reactive compound is peculiar) in d=4.00 and has in d=4.38_
The V of one strength reduction2O5Specific peak.So, catalyst obtained above has the catalysis activity of raising, and can be long-term
Show stability.Similar also has patent documentation 1：Japanese Unexamined Patent Publication 2002-233757 publication, patent documentation 2：Japan is special
Open flat 8-299797 publication, patent documentation 3：Japanese Unexamined Patent Publication 9-194213 publication, patent documentation 4：Japanese Unexamined Patent Application Publication 2004-
No. 504288 publications；CN102066000A.
For improving activity, selectivity and the catalyst life of catalyst, the open one kind of CN200980112659.3 comprises
The coating catalyst of following components：A () carrier, (b) comprises molybdenum oxide or forms the first of the precursor compound of molybdenum oxide
Layer, (c) comprises the second layer of the poly-metal deoxide containing molybdenum and at least one other metal.The molybdenum oxide of preferably ground floor is
MoO3, the poly-metal deoxide that the poly-metal deoxide of the second layer represents for formula II：Mo12BiaCrbX1 cFedX2 eX3 fOy.This is urged
Agent is the application type catalyst including carrier.Goal of the invention is suppression heterogeneously catalysed partial gas phase oxidation acrylic aldehyde is propylene
The coating catalyst inactivation of acid, has improved inactivation performance.This invention is not expressly recited catalyst and is used for being catalyzed propylene
Oxidation acrolein, acrylic acid reactivity worth evaluating data, such as conversion ratio, selectivity, yield etc..CN87103192 is open
A kind of method producing composite oxide catalysts, the Mo-Bi composite oxide catalysts wherein being represented with following chemical formula
Production method includes formation complex in coherent element source compound incorporation Aquo System and carries out heat treatment to this complex,
Using (a) Bi and Na or (b) Bi, Na and X or (c) Bi and X waltherite complex a kind of compound as Bi source, this be combined
At least contain in thing partly that required Na and/or X be wherein：X represents Mg, Ca, Zn, Ce and/or Sm；Y represents K, Rb, Cs and/or Tl；
Z represents B, P, As and/or W；A-K represents respective atomic ratio, as a=12, b=0.5-7, c=0-10, d=0-10, c+d=1-
10th, e=0.05-3, f=0.01-1, g=0-1, h=0.04-0.4, i=0-3, j=0-48, k are one and meet other element oxide states
Number.Solve Bi can in composite oxide catalysts homodisperse problem.α-Bi is contained in catalyst2(MoO4)3、
MoO3Fe2（MoO4）3With β-CoMoO4、y-Bi2MoO6And γ-Bi2MoO6.The open one kind of CN101690900A prepare acrylic aldehyde and
The preparation method of acrylic acid catalyst, catalyst supports thing by active component and inert alumina carrier forms；Active component master
Want component, selected from Mo, Bi, Co and/or Ni and Fe, also comprise the micro unit such as K, Na, Rb, Cs, Mg, Ca, Zn, B, P, W
Element；Wherein active component is represented with following statement formulas：MoaBibCocNidFeeXfYgZhOiIn formula, X represents K, Na, Rb and Cs extremely
Few one kind, Y represents at least one in B, P and W, and Z represents at least one in Mg, Ca, Zn.Active component supports
Ratio on carrier accounts for the 5-70% of overall catalyst weight；Active component is in uneven distribution, CoMoO4、NiMoO4Etc. bivalence gold
The aluminate belonging to is located at the kernel of catalyst activity component；Fe2(MoO4)3And the MoO of free state3Invest the outer layer of kernel；And
The outermost layer of active component is bismuth molybdate, forms the state of core-shell structure copolymer layer distributed.In active component, bivalence molybdate is mainly β
Phase structure, α phase structure content in active component is very low or does not exist.Catalyst has high activity and high stability.
A kind of catalyst producing unsaturated aldehyde and unsaturated carboxylic acid of CN1280036, described production is to be selected from by making at least one
The compound of propylene, isobutene., the tert-butyl alcohol and methyl tertiary butyl ether(MTBE) and oxygen molecule or the gas containing oxygen molecule carry out vapour phase oxygen
Change and realize it is characterised in that this catalyst is a kind of combined oxidation compositions, contain：(A) molybdenum, bismuth and ferrum are contained as master
Want the composite oxides of component, itself be known for described vapor phase catalytic oxidation reaction catalyst, and (B) contain cerium and
Zirconium is as the composite oxides of key component.Catalyst has long catalytic life and makes to operate steadily in the long term and be possibly realized.Its
Middle component (B), is the composite oxides being represented with below general formula (2)：CepZrqFrOy.The zirconium oxide of high degree of dispersion inhibits oxygen
Change the gathering of cerium, to keep the latter during the course of the reaction to the promotion functions significantly absorbing and discharging oxygen, thus accelerating different
The oxidation reaction of butylene, therefore improves catalysis activity.Additionally, further suppress the component causing because of over reduction in time
(A) the irreversible activity of composite oxides reduces (i.e. the stability of composite oxides improves), so that catalytic life is prolonged
Long.This catalysis activity that improve and the catalytic life extending inhibit reaction temperature to raise in time, thus reducing
Molybdenum is in the distillation of hot spot.This catalyst is used for isobutylene oxidation.
CN102489309A discloses a kind of catalyst preparation for producing acrylic aldehyde and renovation process.Catalyst is to have
The composite oxides of following atomic ratios：Mo: Bi: Co: Ni: Fe=10-14: 1.2-2.0: 4.8-5.6: 2-3: 1-2；This catalyst
There is the pore size distribution of more concentration, moderate total pore volume, wherein 5-10nm about mesopore account for more than the 70% of total pore size distribution, shape
Become short and thick pore passage structure, this feature gives catalyst stronger anti-carbon deposition ability, catalyst surface not easy-sintering can
Extend the service life of catalyst.And the renovation process being provided by the present invention, decaying catalyst carries out in an oxidizing atmosphere
1-3 days calcination processing, catalyst activity is suitable with fresh catalyst.CN87103192 produces Mo-Bi-Na composite oxide catalytic
The method of agent product, the method includes mixing coherent element source compound formation complex, then carries out heat treatment, will at least
The bismuth subcarbonate of solid solution partly required Na is as Bi source compound.The activity of catalyst imports specific water by means of Bi and Na
Insoluble compound formed catalyst and greatly improved.
CN1109803 is related to multimetal oxide compositions, and they have two phase structure and comprise molybdenum, hydrogen, one or many
Individual element phosphor, arsenic, boron, germanium and silicon；And it is related to described compositionss in terms of methacrylic acid is prepared by catalytic gas phase oxidation
Purposes, improves activity and selectivity.CN1109802 discloses a kind of multimetal oxide compositions, and they have two phase structure simultaneously
Comprise molybdenum, hydrogen, one or more element phosphors, arsenic, boron, germanium and silicon and copper, improve base acrylic acid activity and selectivity.
CN1298861A is then using the composite oxides adding magnesium, aluminum and silicon.CN1321110A is then respectively with stibium oxide and antimony acetate
Antimony source as active metal composite oxide.To solve under high-load condition, catalytic mechanical intensity is good, active high asking
Topic.CN200410048021.7 discloses a kind of O composite metallic oxide catalyst, and catalyst is by 1. molybdenum, vanadium, copper chief active
Component and 2. requisite at least by antimony and titanium stable component and 3. nickel, ferrum, silicon, aluminum, alkali metal, alkaline-earth metal form
Composite oxides.2. and be 3. wherein can in the range of 120 DEG C to 900 DEG C roasting preparation composite oxides.This catalyst
Show the permanent stability under high activity and good selectivity.The open one kind of CN1121441 is used for by acrylic aldehyde or contains third
Olefine aldehydr gas and a kind of gas of molecule-containing keto carry out oxidation reaction in vapour phase and produce acrylic acid catalyst, this catalyst bag
Include a kind of (A) composite oxides, there is molybdenum and vanadium as base stock, and be suitable to produce by vapor phase catalytic oxidation acrylic aldehyde
Acrylic acid, and a kind of (B) solid peracid, its acid strength (Ho) is not more than -11.93 (Ho≤- 11.93).This invention adopts molybdenum vanadium type
The solid acid that composite oxides are less than -11.93 with a kind of acid strength combines, and improves the low temperature high activity of catalyst.
CN200510059468.9 discloses a kind of acrylic acid catalyst for producing, it is characterized in that, in following formula M oaVbWcCudOx (1)
The oxide of metallic element composition representing and/or the acrylic acid catalyst for producing that composite oxides are necessary catalyst component
In, need the face side controlling tungsten to be partially this catalyst, and/or copper is the core side of this catalyst, partially to improve catalyst
Activity.Tungsten is the face side of this catalyst partially, and/or copper is that the core side of this catalyst is difficult to accurately control partially.
CN102039143A discloses the preparation method that a kind of acrolein oxidation prepares acrylic acid catalyst, a) composite oxide coating
Preparation method：Water-soluble metal salt containing Mo, V, W, Cu, Sb composition is dispersed in water/organic faciess mixing in 30-100 DEG C
In system；Organic solvent and water weight ratio is kept to be 5～50%；Reaction generates composite oxides presoma serosity；Again through steaming
Evaporate, dry, roasting is obtained catalyst activity component；B) the main component of above-mentioned active component, selected from Mo, V, Cu, W, Sb its
In one or more；Wherein active component following formula represents：MoaVbCucWdSbeOf, this catalyst adopts water and lower alcohol
Prepared by mixed system, catalyst has higher specific surface area and special microstructure, has compared with high-ratio surface and is difficult
Come off, and bearing capacity can reach 50% and more than, solve the problems, such as that application type catalyst service life is shorter.
CN1647854 discloses a kind of acrylic acid catalyst of methylacrolein selective oxidation synthesizing methyl, this catalyst
Forming formula is：x(Mo12PaKbSbcCudAseAfDgQhOiMoj)/yZ, Z dilute thermal conducting agent for carrier；Mo, P, K, Sb, Cu and As
It is respectively molybdenum, phosphorus, potassium, antimony, copper and arsenic；A represents at least one of tungsten W, vanadium V, niobium Nb, ferrum Fe and lead Pb element；D represent boron,
At least one of gallium Ga, indium In, germanium Ge and silicon Si element；Q represents at least one of rubidium Rb, caesium Cs and thallium Tl element, this invention
On the one hand improve the activity and selectivity of catalyst by adding Sb, Cu and As；On the other hand pass through to add MoO3And carrier
Heat conduction diluent improving heat stability, heat conductivility and the mechanical strength of catalyst, inhibitory activity component heteropoly acid effectively
The decomposition of salt and reduction beds hot(test)-spot temperature, it is to avoid the loss of Mo and As, extend catalyst service life.
CN1109800 discloses a kind of polymetal oxide materials：In formula, A is Mo12VaXb 1Xc 2Xd 3Xe 4Xf 5Xg 6Ox(coexist
Phase), its part B comprises the crystallite with the X-ray diffraction pattern of at least one following copper molybdate（Give in round parentheses
Close the raw data of X-ray diffraction fingerprint）：Cu3(MoO4)2(OH)2（Lindgrenite, JCPDS-ICDD indexes（1991）Index card
Piece 36-405）, Cu4Mo6O20（A.Moini et al., Inorg.Chem.25（21）（1986）, 3782-3785）, Cu4Mo5O17
（JCPDS-ICDD indexes（1991）Index card 39-181）, etc..CN1462211 be related to one kind prepare containing Mo, V, Cu and
The method of the optional multiple-phase multi-metal oxide materials of other elements.According to this invention, at least one mutually independently shape in advance
Become, and in the precursor material of the plastically deformable being dispersed in another phase.Then this mixture is dried and calcines.Multi-metal oxygen
Compound material is suitable as in catalytic gas phase oxidation organic compound, particularly acrolein oxidation is being become used in acrylic acid
The active material of catalyst.[A] p [B] q [C] r (I), phase A, B in multimetal oxide compositions and C can be unbodied
And/or crystallization.Phase B is advantageously made up of the crystallite of oxometallate, or comprises with X-ray diffraction pattern and enter
And the crystal structure class α-CuMo of the oxometallate crystallite copper molybdate of crystal structure types of at least one following copper molybdate4
[the registration card 22-242 of JCPDS-ICDD card index, (1991)], Cu6Mo5O18[the registration card of JCPCS-ICDD card index
40-865, (1991)], Cu4-xMo3O12, wherein x=0-0.25 [registration card 24-56 and 26- of JCPCS-ICDD card index
547, (1991)], etc..This catalyst is to improve selectivity.
CN1295499 discloses a kind of polymetal oxide materials [A] p [B] q [C] r (I) of formula (I), with containing molybdenum, vanadium,
Copper and antimony and one or more specific other metal simultaneously have the polymetal oxide materials of multicomponent structure as with propylene
The gas phase catalytic oxidation reaction of aldehyde prepares acrylic acid catalyst.In formula, A is Mo12VaX1bX2 cX3 dX4 eX5 fX6 gOx, B is
X1 7CuhHiOy, C is X1 8SbjHkOz, X1For W, Nb, Ta, Cr and/or Ce.Promoter phase B is made up of the crystallite of these copper molybdate
Or contain such copper molybdate crystallite：α-CuMoO4[the reference diffraction in the index card 22-242 of JCPDS-ICDD retrieval 1991
Figure], Cu6Mo5O18[reference diffraction pattern in the index card 40-865 of JCPDS-ICDD retrieval 1991], Cu4-xMo3O12Wherein, x
For 0-0.25 [JCPDS-ICDD retrieval 1991 index card 24-56 and 26-547 in reference diffraction pattern], etc..Region C is permissible
There is metaantimmonic acid copper Cu9Sb4O19The crystallite of structure or Cu4SbO4.5The crystallite of structure.CN1093950 discloses the oxidation of one kind of multiple metals
The compositionss of thing, including Mo, V, W, Cu, Ni of the oxidised form as basis, its premise is between each element composition
There is following ratio：Mo:V=12:1 to 2:1, Mo:W=60:1 to 3:1, Mo:Cu=24:1 to 2:1, Cu:Ni=5:1 to 1:3.
X1It is one or more alkali metal；X2It is one or more alkaline-earth metal；X3It is Cr, Mn, Ce and/or Nb；X4It is Sb and/or Bi；
X5It is Si, Al, Ti and/or Zr.CN1387945 is related to containing the unit in Cu, Mo and at least one W, V, Nb and Ta selected from element
The oxo metal compound of the HT copper molybdate structure type of element, its preparation method, and they in preparation containing molybdenum, vanadium, copper containing
There is answering in the composite metal oxide material having heterogeneous structure of one or more element in elemental tungsten, niobium, tantalum, chromium and cerium
With.CN1394812 poly-metal deoxide, institute used in the catalyst for the catalytic vapor phase oxidation reaction of organic compound
The poly-metal deoxide said contains at least one in Mo, V and element W, Nb, Ti, Zr, Hf, Ta, Cr, Si and Ge, and has spy
Different Three-dimensional atom arrangement.CN1500770 contains molybdenum, vanadium, copper and contains one or more yuan in elemental tungsten, niobium, tantalum, chromium and cerium
The composite metal oxide material having heterogeneous structure of element, they are by answering in catalytic gas phase oxidation of acrolein acrylic acid
With, and the oxo of the HT copper molybdate structure type containing the element in Cu, Mo and at least one W, V, Nb and Ta selected from element
Metal compound.
In addition, under the high temperature conditions, in catalyst, part active component molybdenum loses because of distillation from catalyst surface.Propylene
Aldehyde, air（Oxygen）, the mixed airflow such as nitrogen and vapor wash away the loss of active component that also can make in catalyst.For suppression
The loss of molybdenum distillation causes the decay of activity, and CN1121504 passes through to mix copper component and has specified particle diameter and specific surface area
Zirconium and/or titanium and/or cerium, can suppress dissipation effect and the over reduction of molybdenum composition.Catalyst is included by lower formula (I)
MOaVbWcCudXeYf(I) oxide of metallic element composition representing or composite oxides.CN1445020 adds a small amount of tellurium to play
Stable free molybdenum trioxide and the effect of copper molybdate crystal structure, the sublimation of molybdenum and over reduction have suppressed；
Composite oxides or its oxide with molybdenum, vanadium, copper, tungsten and/or niobium as key component, with other elements composition for the CN1583261
Mixture form catalyst suppress molybdenum loss.
Accordingly, it is desirable to provide acrylic aldehyde, acrylic acid catalyst, catalyst activity component molybdenum etc. are prepared in Propylene Selectivity oxidation
Not easily run off, and activity be mutually not susceptible to phase in version, during acrolein oxidation, temperature of reactor distribution is more reasonable,
Purpose product selectivity and high income, good in economic efficiency, can be reacted under low temperature, high-load condition.
Content of the invention
It is an object of the invention to provide a kind of Propylene Selectivity oxidation produces acrylic aldehyde, acrylic acid poly-metal deoxide is urged
Agent and preparation method thereof.
The present invention relates to a kind of multi-metal-oxide catalyst for propylene oxidation, catalyst contain molybdenum, bismuth, ferrum, cobalt,
Tungsten and potassium element, mainly form by formula M oaBibFecCodWeKfSigAhBiOx（Ⅰ）Represent：Wherein：Mo is molybdenum, and Bi is bismuth, Fe
Ferrum, Co is cobalt, W is tungsten, K is potassium, Si is silicon, silicon be in catalyst add carrier, A be in manganese, boron, lanthanum at least
A kind of element；B is at least one element in magnesium, calcium or barium；O is oxygen；A, b, c, d, e, f, g, h, i represent each unit respectively
Plain atomic ratio, wherein a are 12 numbers, and b is 1.0～7 number, preferably 1.0～6；C is 1～6 number, preferably 1
～5；D is 1～8 number, preferably 1～5；E is 0.2～5 number, and f is 0.1～3.2 number, and g is 0.2～55
A number, preferably 1～20, h is 0.01～2 number, and i is 0～2 number, x be by each oxide oxygen determine
Numerical value.Catalyst also contains strontium titanates, containing molybdenum, bismuth（Ⅰ）Press 90～98% and 0.4～10% mass percent with strontium titanates to mix
Finished catalyst is obtained after kneading, molding, drying, roasting after conjunction.
The preparation method of strontium titanates is not any limitation as, and such as can adopt with the following method：By SrCl2And TiCl4In molar ratio
1.0～1.1 ratio mix homogeneously, adds (NH4)2CO3Solution and ammonia stir, and the pH value that ammonia adjusts solution is
9.5～10.5, then it is spray-dried, gained powder is placed in 1000 in air atmosphere after drying at a temperature of 120～150 DEG C～
1200 DEG C of roastings 4～10 hours, obtain SrTiO finally by methods such as comminution by gas stream, ball millings3.It is also possible that preparation：By carbon
Sour strontium, titanium dioxide are according to SrTiO3Stoichiometric proportion mix homogeneously, add deionized water in formed high dispersive suspension,
Then it is spray-dried, gained powder is placed in 1000～1200 in air atmosphere after drying at a temperature of 120～150 DEG C
DEG C roasting 4～10 hours, obtains SrTiO finally by methods such as comminution by gas stream, ball millings3.
It is highly preferred that the lanthanum CeO2-ZrO2 solid solution that weight/mass percentage composition is 0.1～4 can also be added in catalyst,
Catalyst heat stability and good hydrothermal stability, lanthanum CeO2-ZrO2 solid solution (La of the present inventionxCeyZr1-0.8x-yO2(0<x<1,0
<y<1,0<x+y<1) prepare according to conventional coprecipitation.
It is highly preferred that containing catalyst in catalyst（Ⅰ）92～97%, also strontium titanates 1.5～8%.
The present invention（Ⅰ）Active component lanthanum can be added, lanthanum and bismuth, cobalt can form stable in the catalyst activity component representing
Crystal phase structure, such as BiLa, BiLa2、Co3La2Deng the good dispersion of molybdenum, thus suppress part active component molybdenum from catalyst table
Face loses because of distillation, and active component molybdenum not easily runs off, and before and after catalyst reaction, active component molybdenum content is basically unchanged, and delays to live
Property deterioration rate, catalyst activity and good stability.Lanthanum and molybdenum, cobalt ratio are suitable, formula（Ⅰ）Middle A is lanthanum, and h is 0.05～1.5
A number, i is 0.01～1.2 number, the addition of excessive lanthanum can and bismuth and cobalt competition molybdenum, affect catalyst activity.Urge
Agent mainly forms as formula（Ⅱ）Shown.
MoaBibFecCodWeKfSigLahBiOx（Ⅱ）
The multi-metal-oxide catalyst of the present invention（Ⅰ）Using common preparation method, such as following steps can be adopted
Rapid preparation.
Mo, Bi, the compound of Fe, Co, W, K and formula will be contained（Ⅰ）Middle AhBiThe each element component composition being related to molten
Solution mix homogeneously, form serosity after being co-precipitated, and add in silicon dioxide, aluminium oxide or carborundum in slurry production process
One or more, dry, molding, roasting obtains catalyst（Ⅰ）.
The preparation method of catalyst of the present invention, prepares catalyst (I), strontium titanates including with coprecipitation, by catalyst
(I), strontium titanates is become after mixing with 0.4～10% mass percent by 90～98% after kneading, molding, drying, roasting
Product catalyst.The present invention can also add the lanthanum cerium zirconium oxidation that weight/mass percentage composition is 0.1～4 while adding strontium titanates
Thing solid solution.
Catalyst (I) of the present invention and finished catalyst are required for roasting 3～10h at 400～580 DEG C, compare and do not distinguish
The catalyst of roasting, multiple roasting can improve activity and the stability of catalyst.Can be open roasting can also be closing
Formula roasting, calcination atmosphere can be the noble gases such as helium, nitrogen, argon.
Under Oxygen Condition, molybdenum isoreactivity component is not only easy to run off catalyst under the high temperature conditions, and activity compatible is easy
There is phase in version, activity mutually occurs phase in version to lead to active selectable to be decreased obviously.As active phase CoMoO4It is converted into Co3O4,
Fe2(MoO4)3It is transformed into FeMoO4, α-Bi2(MoO4)3It is changed into γ-Bi2MoO6Deng.
Active component molybdenum in catalyst etc. enables holding and does not run off, and before and after the reaction of molybdenum equal size, basic change is little,
But easily there is phase in version through long-term operation activity compatible.The present invention is by strontium titanates and/or lanthanum CeO2-ZrO2 solid solution
Add in catalyst, make catalyst activity mutually more stable, being not susceptible to phase in version thus improving catalyst activity and selectivity, making
Catalyst long period steady running.
The compound of each component of catalyst of the present invention can be using the nitrate of each element, ammonium salt, sulfate, oxygen
Compound, hydroxide, chloride, acetate etc., such as Lanthanum (III) nitrate, magnesium nitrate, potassium manganate, manganese dioxide, ammonium borate, boric acid, two
Titanium oxide, barium nitrate etc., calcium nitrate, strontium nitrate etc..
It is usually preferred to adopt the molding side such as extrusion molding, granulating and forming, compression molding after catalyst slurry of the present invention is dried
Method processing glomeration, hollow spheres, ellipticity, cylindric, hollow circuit cylinder etc., preferably hollow circuit cylinder or spherical.
The present invention in order to improve intensity, the efflorescence degree of catalyst, can add in the above-mentioned catalyst (I) glass fibre,
One or more in graphite, ceramic or various whisker.
Evaluating catalyst performance index definition is as follows：
Specific embodiment
With specific embodiment, multi-metal-oxide catalyst and preparation method thereof is described below, and this catalyst is in propylene
Selective oxidation prepares acrylic aldehyde（ACR）, acrylic acid（AA）Catalytic performance, but the scope of the present invention be not limited to these enforcement
Example.The propylene that following examples adopt is propylene content >=99.6%（Volume fraction）High concentration propylene.The analysis of product form
Method adopts method generally in the art.
Embodiment 1
1. prepare catalyst（Ⅰ）
Under agitation, 197 grams of ammonium molybdates are taken to be dissolved in 1000ml pure water（More than 65 DEG C of water temperature）, obtain serosity
（1）, then take 73 grams of cobalt nitrates, 1.88 grams of potassium nitrate, 6.86 grams of magnesium nitrates, 112.7 grams of ferric nitrates, 15.1 grams of Lanthanum (III) nitrates to be dissolved in
In 500ml pure water（More than 65 DEG C of water temperature）, it is thoroughly mixed uniformly, obtain serosity（2）.Take 45.1 grams of bismuth nitrate again,
It is dissolved under stirring condition in dust technology, obtain serosity（3）.Then, serosity（1）With serosity（2）Mixing, obtains serosity（4）, then
By serosity（3）Add serosity（4）In, obtain active component serosity（a）.In active component serosity（a）11.7 grams of dioxies of middle addition
SiClx powder and 4 grams of graphite, 80 DEG C of strong stirrings carry out coprecipitation reaction post-heating drying, little with 160 DEG C of heat treatments 3 in nitrogen
When, dry rear 550 DEG C of roastings 4 hours for 105 DEG C, then grind to form less than 40 μm of fine powder, prepared catalyst again（Ⅰ）, main group
Become：Mo12Bi1Fe3Co2.7W2K0.2Si2.1Mg0.4La0.5Ox.
Weigh a certain amount of cerous nitrate, Lanthanum (III) nitrate, zirconium nitrate according to stoichiometric proportion, be configured to mixed solution, continuous
In the case of stirring, to mixed solution and dripping ammonia spirit so as to carry out coprecipitation reaction, then through sucking filtration, 120 DEG C of bakings
Dry, 950 DEG C of roastings 10 hours, then grind to form less than 40 μm of fine powder, prepared Ce again0.6Zr0.3La0.22O2,
Ce0.5Zr0.4La0.2O2, Ce0.7Zr0.2La0.31O2.
By strontium carbonate, titanium dioxide according to SrTiO3Stoichiometric proportion mix homogeneously, add formed in deionized water high
Scattered suspension, is then spray-dried to it, and gained powder is placed in air gas after drying at a temperature of 120～150 DEG C
1100 DEG C of roastings 10 hours in atmosphere, obtain SrTiO finally by ball milling3.
Take catalyst（Ⅰ）93 parts, 4.5 parts of metatitanic acid strontium oxide, lanthanum CeO2-ZrO2 solid solution Ce0.5Zr0.4La0.2O22.5
Part, plus deionized water mediates in kneader, extrusion molding is the hollow columnar granule of φ 4.5 × 5mm, does under the conditions of 120 DEG C
Dry, roasting at 450 DEG C obtains catalyst 1 in 6.5 hours.
Embodiment 2
The preparation of catalyst 2
Preparation process and primary raw material with embodiment 1 catalyst 1 are identical, obtain final product catalyst within 3 hours through 550 DEG C of roastings
（Ⅰ）, mainly consist of：Mo12Bi5Fe5Co6W3K2Ba0.3Si1.2B0.5Ox.Take catalyst（Ⅰ）98 parts, 1.5 parts of metatitanic acid strontium oxide,
Lanthanum CeO2-ZrO2 solid solution Ce0.5Zr0.4La0.2O20.5 part, plus deionized water mediates in kneader, extrusion molding is φ
The hollow columnar granule of 4.5 × 5mm, is dried under the conditions of 120 DEG C, and roasting at 500 DEG C obtains catalyst 2 in 4.5 hours.
Embodiment 3
Preparation process and primary raw material with embodiment 1 catalyst 1 are identical, obtain final product catalyst within 6 hours through 400 DEG C of roastings
（Ⅰ）.Mainly consist of：Mo12Bi7Fe1Co8W0.3K3.2Si5.1Ca0.3Mn1.8Ox, take catalyst（Ⅰ）95 parts, metatitanic acid strontium oxide 4
Part, lanthanum CeO2-ZrO2 solid solution Ce0.6Zr0.3La0.22O21 part, plus deionized water mediates in kneader, extrusion molding is φ
The hollow columnar granule of 4.5 × 5mm, is dried under the conditions of 120 DEG C, and roasting at 530 DEG C obtains catalyst 3 in 5 hours.
Embodiment 4
Preparation process and primary raw material with embodiment 1 catalyst 1 are identical, through 5 hours catalyst of 480 DEG C of roastings（Ⅰ）.Main
Consist of：Mo12Bi3.5Fe4Co4.5W1K0.5Si2.4Mn0.1Mg0.2Ox.Take catalyst（Ⅰ）91 parts, 5.5 parts of metatitanic acid strontium oxide,
Lanthanum CeO2-ZrO2 solid solution Ce0.7Zr0.2La0.31O23.5 parts, plus deionized water mediates in kneader, extrusion molding is φ
The hollow columnar granule of 4.5 × 5mm, is dried under the conditions of 120 DEG C, and roasting at 500 DEG C obtains catalyst 4 in 5 hours.
Embodiment 5
Preparation process and primary raw material with embodiment 1 catalyst 1 are identical, obtain final product catalyst within 3 hours through 560 DEG C of roastings
（Ⅰ）.Mainly consist of：Mo12Bi2.2Fe2.3Co1.2W5K1.4Si1.6La1.2Ba0.3Ox.Take catalyst（Ⅰ）97 parts, strontium titanates aoxidizes
3 parts of thing, plus deionized water mediates in kneader, extrusion molding is the hollow columnar granule of φ 4.5 × 5mm, under the conditions of 120 DEG C
It is dried, roasting at 480 DEG C obtains catalyst 5 in 6 hours.
Embodiment 6
Preparation process and primary raw material with embodiment 1 catalyst 1 are identical, obtain final product catalyst within 4 hours through 500 DEG C of roastings
（Ⅰ）.Mainly consist of Mo12Bi3Fe2Co1.7W4K1.0Si1.0La2.1Ba0.3Ox.Take catalyst（Ⅰ）95 parts, metatitanic acid strontium oxide 5
Part, plus deionized water mediates in kneader, extrusion molding is the hollow columnar granule of φ 4.5 × 5mm, does under the conditions of 120 DEG C
Dry, roasting at 520 DEG C obtains catalyst 6 in 5 hours.
Comparative example 1
According to the main composition and ratio preparation comparative catalyst 1 of embodiment 1, but lanthanum cerium zirconium is not with solid solution, oxide
Form add catalyst, strontium titanates is not to be added in the form of Whole Oxygen compound, but prepares catalyst with coprecipitation method,
Reaction condition is with the appreciation condition of catalyst 1.Comparative catalyst 1 mainly consists of：
Mo12Bi1Fe3Co2.7W2K0.2Si2.1Mg0.4Ce0.5Zr0.4La0.2Ti0.2Sr0.2La0.5Ox.
Comparative example 2
According to the main composition and ratio preparation comparative catalyst 2 of comparative example 1, but lanthanum cerium zirconium is not with solid solution, oxide
Form add catalyst, do not contain strontium titanates in catalyst, but catalyst prepared with coprecipitation method, reaction condition is with being catalyzed
The appreciation condition of agent 1.Comparative catalyst 2 mainly consists of：
Mo12Bi1Fe3Co2.7W2K0.2Si2.1Mg0.4Ce0.5Zr0.4La0.2La0.5Ox.
Oxidation reaction
Fixed bed single tube reactor internal diameter 25mm, inside sets thermocouple, loads 40ml along propylene feed orienting response device bed
Above-mentioned catalyst or comparative example catalyst, 312 DEG C of salt bath heating temperature.Tube inlet sentences air speed 1100h from the reactions above-1Import
Propylene 11 volume %, air 75 volume %, the mixed gas of vapor 14 volume %.The performance of catalyst is as shown in table 1.Reaction
24 hours and 2000 hours, load not higher than 364 DEG C of beds hot localised points temperature of the present invention, embodiment catalyst activity
Component molybdenum etc. not easily runs off, and activity is mutually not susceptible to phase in version, and during acrolein oxidation, reaction bed temperature divides
Cloth is more reasonable.Acrylic aldehyde and acrylic acid total recovery more than 91.4%, catalyst activity component Stability Analysis of Structures, catalyst has good
Good water repelling property, catalyst performance stabilised, make catalyst long period steady running.Comparative example catalyst choice is poor, propylene
Aldehyde, acrylic acid yield are low.Temperature of reactor distribution is more reasonable, purpose product selectivity and high income, good in economic efficiency, can be
Reacted under low temperature, high-load condition.Comparative example catalyst propylene conversion and acrolein selectivity are low, acrylic aldehyde acrylic acid
Yield is low.
Embodiment 4 catalyst is in 312 DEG C of salt bath heating temperature, air speed 1100h-1, propylene 11 volume %, air 69 body
React 24 hours and 500 hours under conditions of long-pending %, vapor 20 volume %, respectively 363 DEG C of bed hot localised points temperature,
361 DEG C, propylene conversion 99.0%, 98.8%, acrolein selectivity 88.0%, 88.2%, acrylic aldehyde yield 81.4%, 81.6%, third
Olefine aldehydr+acrylic acid yield 91.5%, 92.4%.Temperature Distribution is more reasonable, catalyst activity component Stability Analysis of Structures, is conducive to being catalyzed
Agent long period steady running.Embodiment 4 and 6 catalyst are in 312 DEG C of salt bath heating temperature, air speed 1100h-1, propylene 11 volume %,
Salt temperature is adjusted again to 350 DEG C after stablizing 6 hours under conditions of air 69 volume %, vapor 20 volume %（Stop propylene）,
It is down to 312 DEG C again after 10 hours, embodiment 4 and 6 is under similarity condition（312 DEG C of salt bath heating temperature, air speed 1100h-1、
Propylene 11 volume %, air 69 volume %, vapor 20 volume %）Reaction 24 hours, bed hot localised points temperature is respectively 360
DEG C, 354 DEG C, propylene conversion 99.1%, 98.0%, acrolein selectivity 88.0%, 85.1%, acrylic aldehyde yield 81.3%, 76.5%,
Acrolein+acrylic acid yield 91.4%, 87.5%.Through vapor 20 volume %, salt bath heating temperature 350 DEG C of hydrothermal treatment consists
Under the conditions of, with respect to embodiment 6, embodiment 4 catalyst heat stability and good hydrothermal stability, catalyst activity component structure is steady
Fixed, meet catalyst long period steady running.
Table 1 reacts 24 hours post-evaluation results
Table 2 reacts 2000 hours post-evaluation results
Claims (12)
1. a kind of catalyst for propylene oxidation is it is characterised in that catalyst contains molybdenum, bismuth, ferrum, cobalt, tungsten and potassium element, main
Form by formula M oaBibFecCodWeKfSigAhBiOx(I) represent, wherein：Silicon is carrier, and A is in manganese, boron, lanthanum
At least one element；B is at least one element in magnesium, calcium or barium；A, b, c, d, e, f, g, h, i represent each element respectively
Atomic ratio, wherein a are 12 numbers, and b is 1.0～7 number, and c is 1～6 number, and d is 1～8 number, e
It is 0.2～5 number, f is 0.1～3.2 number, g is 0.2～55 number, h is 0.01～2 number, i
It is 0～2 number, x is the numerical value being determined by the oxygen of each oxide；Catalyst also contains strontium titanates, described main composition and
Strontium titanates obtains finished product after kneading, molding, drying, roasting after mixing by 90～98% and 0.4～10% mass percent and urges
Agent.
2. catalyst according to claim 1 is it is characterised in that it is 0.1～4% that catalyst also contains weight/mass percentage composition
Lanthanum CeO2-ZrO2 solid solution, the quality hundred of described main composition, described strontium titanates and described lanthanum CeO2-ZrO2 solid solution
Content sum is divided to be absolutely.
3. catalyst according to claim 1 is it is characterised in that contain described main composition 92～97%, also in catalyst
There is strontium titanates 1.5～8%.
4. it is characterised in that leading to A in formula I is lanthanum, h is of 0.05～1.5 to catalyst according to claim 1
Number, i is 0.01～1.2 number, and catalyst mainly forms as shown in logical formula II：MoaBibFecCodWeKfSigLahBiOx
(Ⅱ).
5. catalyst according to claim 4 is it is characterised in that lead to the number that b in formula I is 1.0～6.
6. catalyst according to claim 4 is it is characterised in that lead to the number that c in formula I is 1～5.
7. catalyst according to claim 4 is it is characterised in that lead to the number that d in formula I is 1～5, g is 1～20
One number.
8. catalyst according to claim 1 is it is characterised in that the preparation method of described main composition comprises the steps：
Contained Mo, Bi, A in the compound of Fe, Co, W, K and logical formula I respectivelyhBiThe each element component composition being related to dissolves and mixes
Close uniformly, after being co-precipitated, form serosity, in slurry production process, add silicon dioxide, dry, molding, roasting obtains described master
Form.
9. catalyst according to claim 8 it is characterised in that described be roasted at 400～580 DEG C roasting 3～
10h, and adopt open roasting or enclosed roasting, calcination atmosphere is helium, nitrogen or argon.
10. catalyst according to claim 8 is it is characterised in that described each element component composition is the nitre of each element
One of hydrochlorate, ammonium salt, sulfate, oxide, hydroxide, chloride or acetate.
The preparation method of catalyst described in 11. claim 1 is it is characterised in that include described main group with coprecipitation preparation
One-tenth, metatitanic acid strontium oxide, described main composition, metatitanic acid strontium oxide press 90～98% and 0.4～10% mass percent mixing,
Obtain finished catalyst after kneading, molding, drying, roasting.
12. the preparation method of catalyst is it is characterised in that described main composition, metatitanic acid strontium oxide according to claim 11
Mix by 90～98% and 0.4～10% mass percent, through kneading, molding, drying and roasting 3 at 400～580 DEG C
Finished catalyst is obtained, using open roasting or enclosed roasting, calcination atmosphere is helium, nitrogen or argon after～10h.
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