CN104646016B - Unsaturated aldehyde oxidation catalyst and preparation method thereof - Google Patents
Unsaturated aldehyde oxidation catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN104646016B CN104646016B CN201310585299.7A CN201310585299A CN104646016B CN 104646016 B CN104646016 B CN 104646016B CN 201310585299 A CN201310585299 A CN 201310585299A CN 104646016 B CN104646016 B CN 104646016B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- oxide
- lanthanum
- formula
- catalyst according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 179
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 38
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract 3
- 230000003647 oxidation Effects 0.000 title claims description 31
- 238000002360 preparation method Methods 0.000 title claims description 19
- 239000010949 copper Substances 0.000 claims abstract description 58
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 52
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000011733 molybdenum Substances 0.000 claims abstract description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 claims abstract description 30
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 24
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 20
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 19
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 15
- 239000006104 solid solution Substances 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen 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
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 239000011777 magnesium Substances 0.000 claims abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 4
- HLRPCWSWHIWFHM-UHFFFAOYSA-N cerium(3+) lanthanum(3+) oxygen(2-) zirconium(4+) Chemical compound [O--].[O--].[O--].[O--].[O--].[Zr+4].[La+3].[Ce+3] HLRPCWSWHIWFHM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011591 potassium Substances 0.000 claims abstract description 4
- 229910016300 BiOx Inorganic materials 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 34
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 238000000975 co-precipitation Methods 0.000 claims description 8
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052792 caesium Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 claims description 2
- NXGASACSZHOEHS-UHFFFAOYSA-N cerium lanthanum zirconium Chemical compound [Zr].[La].[Ce] NXGASACSZHOEHS-UHFFFAOYSA-N 0.000 claims 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052710 silicon Inorganic materials 0.000 abstract description 11
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 9
- 239000010703 silicon Substances 0.000 abstract description 9
- 239000010936 titanium Substances 0.000 abstract description 8
- 229910052719 titanium Inorganic materials 0.000 abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 4
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 32
- 230000000694 effects Effects 0.000 description 32
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 28
- 239000012071 phase Substances 0.000 description 28
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 26
- 239000002131 composite material Substances 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000007789 gas Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 13
- 239000002184 metal Substances 0.000 description 12
- 239000010955 niobium Substances 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 9
- 239000003377 acid catalyst Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 9
- 229910052758 niobium Inorganic materials 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229910052684 Cerium Inorganic materials 0.000 description 7
- 150000001299 aldehydes Chemical class 0.000 description 7
- 229910052785 arsenic Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- IKUPISAYGBGQDT-UHFFFAOYSA-N copper;dioxido(dioxo)molybdenum Chemical compound [Cu+2].[O-][Mo]([O-])(=O)=O IKUPISAYGBGQDT-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910052715 tantalum Inorganic materials 0.000 description 6
- 229910018864 CoMoO4 Inorganic materials 0.000 description 5
- 229910015667 MoO4 Inorganic materials 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-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
- 238000001125 extrusion 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
- 239000002245 particle Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 229910017354 Fe2(MoO4)3 Inorganic materials 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910052732 germanium Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910052701 rubidium Inorganic materials 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229910002900 Bi2MoO6 Inorganic materials 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-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
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910000410 antimony oxide 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
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 230000001404 mediated effect Effects 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- -1 oxo metal compound Chemical class 0.000 description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 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
- 230000008901 benefit Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000001427 coherent effect Effects 0.000 description 2
- 230000008021 deposition Effects 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
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 125000000468 ketone group Chemical group 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals 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
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000009418 renovation Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation 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
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- 229910017010 Fe2 (MoO4)3 Inorganic materials 0.000 description 1
- 229910015142 FeMoO4 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
- 229910002335 LaNi5 Inorganic materials 0.000 description 1
- 206010054949 Metaplasia Diseases 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
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229940036348 bismuth carbonate Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 239000003426 co-catalyst Substances 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
- 229940116318 copper carbonate Drugs 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 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
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion 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
- 238000011049 filling 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
- 238000000227 grinding Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
- 239000011261 inert gas Substances 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
- 230000015689 metaplastic ossification Effects 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
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- IRPDISVJRAYFBI-UHFFFAOYSA-N nitric acid;potassium Chemical compound [K].O[N+]([O-])=O IRPDISVJRAYFBI-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 230000036961 partial effect Effects 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
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 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
- 239000004575 stone Substances 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000001629 suppression Effects 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
- 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
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a multi-metal oxide catalyst, which contains molybdenum, vanadium, tungsten, copper, nickel and antimony and mainly comprises the general formula Moa′Vb′Wc′Cud′NifSbgAhBiOx(I) is shown in the specification, wherein: silicon is added as carrier, A is at least one of potassium, titanium and zirconiumAn element; b is at least one element selected from magnesium, iron and lanthanum; o is oxygen; the catalyst also contains a lanthanum cerium zirconium oxide solid solution. The catalyst of the invention is used for the selective oxidation reaction of unsaturated aldehyde to produce corresponding unsaturated acid.
Description
Technical field
The present invention relates to a kind of unsaturated aldehyde oxidation catalyst and preparation method thereof, selected for methacrylaldehyde or MAL
The selecting property oxidation corresponding unsaturated acids of production, is particularly suited for being catalyzed prepared by acrolein oxidation acrylic acid.
Background technology
Industrial methacrylaldehyde or the oxidation of aldehydes reaction unit for preparing corresponding unsaturated acids of metering system are mainly many reactions
Pipe, is ensureing that catalyst is not sintered, on the premise of long service life, selectivity and purpose product yield, section improved as far as possible
Save raw material, if even if feed stock conversion, methacrylaldehyde acrylic acid yield improve 0.1~0.5 percentage point, the amount of the product for obtaining with
The level of hundreds of~thousands of tons of increases, and its economic benefit is also very considerable.
It is mainly molybdenum system multicomponent catalyst on propylene fraction oxidation acrolein, acrylic acid catalyst.Due to propylene
It is strong exothermal reaction that selective oxidation prepares the acrylic acid reaction of methacrylaldehyde, so the big water of specific heat is passed through 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, part active component molybdenum loses from catalyst surface because of distillation in catalyst.Active component molybdenum
Loss causes to reduce the active of catalyst, selectivity, intensity and service life, and molybdenum in the deposition in reaction system downstream, resistance
Plug pipeline influences the long-term operation of system.
In addition, active component molybdenum in catalyst etc. is enabled to keep not being lost in, basic change before and after the reaction of molybdenum equal size
Less, but easily there is phase in version by 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, plays selective oxidation；Fe2
(MoO4)3Play redox facilitation；CoMoO4And NiMoO4Play Stability Analysis of Structures.However, using coprecipitation method system
Standby catalyst is more due to component, and process is complicated, catalyst stabilization difference, although initial activity is very high, inactivation is fast.Cause many
Component Mo-Bi-Co-Fe-O catalyst and Mo-V-O catalyst inactivation and stability decline factor have a lot, including because
The sublimation of Mo components and the change of irreversible crystalline phase etc. caused by local abnormal high temperature (focus).These factors can all draw
The change of specificity of catalyst is played, is caused the reduction of catalyst activity and is shortened the service life of catalyst.Urged by 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, being the loss of suppression molybdenum, CN1583261 discloses one kind
It is selectively oxidized the composition metal of reaction in the gas phase with a kind of gas of molecule-containing keto for the gas containing unsaturated aldehyde
Oxide catalyst, its catalyst constitutes and is：[MoaVbCucXd]Ym[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 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 to be selected from iron
With a kind of element of nickel, Z2It is at least to be selected from silicon, aluminium, a kind of element of alkali and alkaline earth metal ions, a, b, c, d, e, f, g and x
The atomic ratio number of its element is represented, 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 with ammonium metavanadate and
Copper nitrate, and with low price barium oxide and/or low price Cu oxide part replace ammonium metavanadate 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 in d=4.00 have a strengthened peak (vanadium-molybdenum reactive compound is peculiar) and have one in d=4.38
The V of individual remitted its fury2O5Specific peak.So, catalyst obtained above has the catalysis activity for improving, and can long-term table
Reveal stability.Similar also has patent document 1：Japanese Unexamined Patent Publication 2002-233757 publications, patent document 2：Japanese Unexamined Patent Publication
Flat 8-299797 publications, patent document 3：Japanese Unexamined Patent Publication 9-194213 publications, patent document 4：Japanese Unexamined Patent Application Publication 2004-
No. 504288 publications；CN102066000A.
To improve the active of catalyst, selectivity and catalyst life, CN200980112659.3 discloses one kind and includes
The coating catalyst of following components：(a) carrier, (b) comprising molybdenum oxide or the precursor compound for forming molybdenum oxide first
Layer, (c) includes the second layer containing molybdenum and the poly-metal deoxide of at least one other metals.It is preferred that the molybdenum oxide of ground floor is
MoO3, the poly-metal deoxide of the second layer is the poly-metal deoxide that formula II is represented：Mo12BiaCrbX1 cFedX2 eX3 fOy.This is urged
Agent is to include the application type catalyst of carrier.Goal of the invention is to suppress heterogeneously catalysed partial gas phase oxidation methacrylaldehyde for propylene
The coating catalyst inactivation of acid, with improved inactivation performance.The invention does not have catalyst is expressly recited for being catalyzed propylene
Oxidation acrolein, such as acrylic acid reactivity worth evaluating data, conversion ratio, selectivity, yield etc..CN87103192 is disclosed
A kind of method for producing composite oxide catalysts, wherein the Mo-Bi composite oxide catalysts represented with following chemical formula
Production method includes being heat-treated formation compound in coherent element source compound incorporation Aquo System and to the compound,
Using (a) Bi and Na or (b) Bi, Na and X or (c) Bi and X waltherite compound a kind of compound as Bi sources, this be combined
In thing at least containing Na and/or X needed for part 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 the problems, such as that Bi can be dispersed in composite oxide catalysts.Contain α-Bi in catalyst2(MoO4)3、
MoO3Fe2（MoO4）3With β-CoMoO4、y-Bi2MoO6And γ-Bi2MoO6.CN101690900A disclose one kind prepare methacrylaldehyde and
The preparation method of acrylic acid catalyst, catalyst supports thing by active component and inert alumina carrier is constituted；Active component master
Component is wanted, selected from Mo, Bi, Co and/or Ni and Fe, also comprising 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 that, selected from least one in B, P and W, Z is represented selected from least one in Mg, Ca, Zn.Active component is supported
Ratio on carrier accounts for the 5-70% of overall catalyst weight；Active component is in uneven distribution, CoMoO4、NiMoO4Etc. divalence gold
The aluminate of category 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.Divalence molybdate is mainly β in active component
Phase structure, content is very low in active component or does not exist for α phase structures.Catalyst has high activity and high stability.
A kind of catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid of CN1280036, described production is selected from by making at least one
The compound and oxygen molecule of propylene, isobutene, the tert-butyl alcohol and methyl tertiary butyl ether(MTBE) or the gas containing oxygen molecule carry out vapour phase oxygen
Change and realize, it is characterised in that the catalyst is a kind of combined oxidation compositions, is contained：(A) containing molybdenum, bismuth and iron as master
Want the composite oxides of component, itself be the known catalyst for vapor phase catalytic oxidation reaction, and (B) containing cerium and
Zirconium as key component composite oxides.Catalyst has catalytic life long and makes it possible to operate steadily in the long term.Its
Middle component (B), is the composite oxides represented with below general formula (2)：CepZrqFrOy.The zirconium oxide of high degree of dispersion inhibits oxygen
Change the aggregation of cerium, it is different so as to accelerate to keep the latter during the course of the reaction to significantly absorbing and discharging the promotion functions of oxygen
The oxidation reaction of butylene, therefore improve catalysis activity.Additionally, further suppress the component because causing with time over reduction
(A) the irreversible activity of composite oxides reduces (i.e. the stability of composite oxides is improved), so that catalytic life is prolonged
It is long.This catalysis activity that improve and the catalytic life for extending inhibit reaction temperature to be raised with the time, so as to reduce
Distillation of the molybdenum in hot spot.The catalyst is used for isobutylene oxidation.
CN102489309A discloses a kind of catalyst preparation and renovation process for producing methacrylaldehyde.Catalyst be with
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；The catalyst
With the pore size distribution more concentrated, the mesopore of moderate total pore volume, wherein 5-10nm or so accounts for more than the 70% of total pore size distribution, shape
Into short and thick pore passage structure, this feature assigns catalyst stronger anti-carbon deposition ability, catalyst surface not easy-sintering, can
Extend the service life of catalyst.And passing through the renovation process that the present invention is provided, decaying catalyst is carried out in an oxidizing atmosphere
1-3 days calcination processings, catalyst activity is suitable with fresh catalyst.CN87103192 produces Mo-Bi-Na composite oxide catalytics
The method of agent product, the method includes that mixing coherent element source compound forms compound, then is heat-treated, will at least
The basic bismuth carbonate of Na is used as Bi source compounds needed for solid solution part.The activity of catalyst imports specific water by means of Bi and Na
Insoluble compound formed catalyst and be able to greatly improve.
CN1109803 is related to multimetal oxide compositions, and they have two phase structure and comprising molybdenum, hydrogen, one or many
Individual element phosphor, arsenic, boron, germanium and silicon；And it is related to the composition 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
Comprising molybdenum, hydrogen, one or more element phosphors, arsenic, boron, germanium and silicon and copper, base acrylic acid activity and selectivity is improved.
CN1298861A is then the composite oxides using addition magnesium, aluminium and silicon.CN1321110A is then respectively with antimony oxide and antimony acetate
As the antimony source of active metal composite oxide.To solve under high-load condition, catalytic mechanical intensity is good, and activity is high to ask
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. it is essential at least by antimony and titanium stable component and 3. nickel, iron, silicon, aluminium, alkali metal, alkaline-earth metal are constituted
Composite oxides.Wherein 2. and 3. it is the composite oxides that preparation can be calcined in the range of 120 DEG C to 900 DEG C.The catalyst
Show the permanent stability under high activity and good selectivity.CN1121441 discloses a kind of for by methacrylaldehyde or containing third
Olefine aldehydr gas carries out oxidation reaction in vapour phase and produces acrylic acid catalyst, the catalyst bag with a kind of gas of molecule-containing keto
A kind of (A) composite oxides are included, with molybdenum and vanadium as base stock, and is suitable to by vapor phase catalytic oxidation methacrylaldehyde to produce
Acrylic acid, and a kind of (B) solid peracid, its acid strength (Ho) are not more than -11.93 (Ho≤- 11.93).The invention uses molybdenum vanadium type
Composite oxides are combined with a kind of solid acid of acid strength no more than -11.93, improve 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 the metallic element composition of expression and/or the acrylic acid catalyst for producing that composite oxides are necessary catalyst component
In, it is necessary to control the face side that tungsten is the catalyst partially, and/or copper is the core side of the catalyst partially, to improve catalyst
Activity.Tungsten is the face side of the catalyst partially, and/or copper is that the core side of the catalyst is difficult accurate 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 into water/organic in 30-100 DEG C to mix
In system；It is 5~50% to keep organic solvent and water weight ratio；Reaction generation composite oxides presoma slurries；Again by steaming
Evaporate, dry, being calcined prepared 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 is represented with following formula：MoaVbCucWdSbeOf, the catalyst is using water and lower alcohol
Prepared by mixed system, catalyst has specific surface area and special microstructure higher, with compared with high-ratio surface and being 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 MAL selective oxidation synthesizing methyl, the catalyst
Constituting formula is：x(Mo12PaKbSbcCudAseAfDgQhOiMoj)/yZ, Z are that carrier dilutes thermal conducting agent；Mo, P, K, Sb, Cu and As
Respectively molybdenum, phosphorus, potassium, antimony, copper and arsenic；A represents at least one of tungsten W, vanadium V, niobium Nb, iron 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, the invention
On the one hand the activity and selectivity of catalyst is improved by adding Sb, Cu and As；On the other hand by adding MoO3And carrier
Heat conduction diluent improves heat endurance, heat conductivility and the mechanical strength of catalyst, effectively inhibitory activity component heteropoly acid
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：A is Mo in formula12VaXb 1Xc 2Xd 3Xe 4Xf 5Xg 6Ox(coexist
Phase), crystallites of its part B comprising the X-ray diffraction pattern with least one following copper molybdate（Given in round parentheses
Close the firsthand information 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）Card index 39-181）, etc..CN1462211 be related to one kind prepare containing Mo, V, Cu and
The method of the multiple-phase multi-metal oxide materials of other optional elements.According to the invention, at least one mutually independently advance shape
Into, and be dispersed in the precursor material of the plastically deformable of another phase.Then the mixture is dried and calcines.Multi-metal oxygen
Compound material is suitable as in catalytic gas phase oxidation organic compound, particularly by acrolein oxidation into used in acrylic acid
The active material of catalyst.[A] p [B] q [C] r (I), phase A, B and C in multimetal oxide compositions can be unbodied
And/or crystallization.Advantageously it is made up of the crystallite of oxometallate for phase B, or comprising with X-ray diffraction pattern and entering
And the crystal structure class α-CuMo of the oxometallate crystallite copper molybdate of the crystal structure types of at least one following copper molybdate4
[the registration card 22-242 of JCPDS-ICDD card indexs, (1991)], Cu6Mo5O18[the registration card of JCPCS-ICDD card indexs
40-865, (1991)], Cu4-x Mo3O12, wherein x=0-0.25 [the registration card 24-56 and 26- of JCPCS-ICDD card indexs
547, (1991)], etc..The catalyst is to improve selectivity.
CN1295499 discloses polymetal oxide materials [A] p [B] q [C] r (I) of formula (I) a kind of, 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, X1It is W, Nb, Ta, Cr and/or Ce.Co-catalyst phase B is made up of the crystallite of these copper molybdates
Or contain such copper molybdate crystallite：α-CuMoO4[the reference diffraction in the index card 22-242 of JCPDS-ICDD retrievals 1991
Figure], Cu6Mo5O18[reference diffraction pattern in the index card 40-865 of JCPDS-ICDD retrievals 1991], Cu4-xMo3O12Wherein, x
It is 0-0.25 [reference diffraction pattern in the index card 24-56 and 26-547 of JCPDS-ICDD retrievals 1991], etc..Region C can be with
With metaantimmonic acid copper Cu9Sb4O19The crystallite or Cu of structure4SbO4.5The crystallite of structure.CN1093950 discloses the oxidation of one kind of multiple metals
The composition of thing, including the oxidised form as basis Mo, V, W, Cu, Ni, with the proviso that 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 contain 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 types of element, its preparation method, and they are preparing containing molybdenum, vanadium, copper and are containing
Have in elemental tungsten, niobium, tantalum, chromium and cerium one or more element have in the composite metal oxide material of heterogeneous structure should
With.The poly-metal deoxide that CN1394812 is used in for the catalyst of the catalytic vapor phase oxidation reaction of organic compound, institute
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 with 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 for having heterogeneous structure of element, their answering in by catalytic gas phase oxidation of acrolein acrylic acid
With, and the HT copper molybdate structure types containing the element in Cu, Mo and at least one W, V, Nb and Ta selected from element oxo
Metal compound.
In addition, under the high temperature conditions, part active component molybdenum loses from catalyst surface because of distillation in catalyst.Propylene
Aldehyde, air（Oxygen）, the mixed airflow such as nitrogen and vapor wash away the loss of active component that can also make in catalyst.To suppress
Losss of molybdenum distillation causes active decay, and CN1121504 is by mixing copper component and with specified particle diameter and specific surface area
Zirconium and/or titanium and/or cerium, can suppress the dissipation effect and over reduction of molybdenum composition.Catalyst is included by lower formula (I)
MOaVbWcCudXeYf(I) oxide or composite oxides of the metallic element composition for representing.CN1445020 adds a small amount of tellurium to play
The effect of the free molybdenum trioxide of stabilization and copper molybdate crystal structure, the sublimation and over reduction of molybdenum have suppressed；
CN1583261 with molybdenum, vanadium, copper, tungsten and/or niobium as key component, with other elements constitute composite oxides or its oxide
Mixture composition catalyst suppress molybdenum loss.
Accordingly, it is desirable to provide methacrylaldehyde or MAL selective oxidation produce the catalyst of corresponding unsaturated acids
Agent active component molybdenum etc. is not easily runed off, and activity is mutually not susceptible to phase in version, makes methacrylaldehyde long period stably selective oxygen
Metaplasia produces acrylic acid, during acrolein oxidation, is reacted under low temperature, high-load condition, and improve mesh as far as possible
Product selectivity and yield, to obtain bigger economic benefit.
The content of the invention
Corresponding unsaturated acids is produced it is an object of the invention to provide a kind of methacrylaldehyde or MAL selective oxidation
Catalyst and preparation method thereof.It is particularly suited for acrolein selectivity oxidation and prepares acrylic acid.
The present invention relates to a kind of unsaturated aldehyde oxidation catalyst, the catalyst contains molybdenum, vanadium, tungsten, copper, nickel and antimony element,
Mainly constitute by formula M oa′Vb′Wc′Cud′NifSbgAhBiOx（Ⅰ）Represent, wherein：Mo is molybdenum, and V is alum, and W is tungsten, and Cu is copper, Ni
It is nickel, Sb is antimony, and Si is silicon, and silicon is the carrier of addition in catalyst, and A is selected from least one element in potassium, zinc, caesium；B is
At least one element in selected from magnesium, iron, lanthanum；O is oxygen；A ', b ', c ', d ', f, g, h, i represent each element atomic ratio respectively, its
Middle a ' is a number of 12-14, and b ' is a number of 2-7, preferably 2-5；C ' is a number of 1-5, preferably 1-3.5；D ' is 1-6
A number, preferably 1.5-4；F is a number of 0.5-5, and g is a number of 0.1-5, and h is a number of 0.1-2.5, and i is
One number of 0.1-3.5, x is the numerical value determined by the oxygen of each oxide.Catalyst also contains metatitanic acid strontium oxide, containing molybdenum, vanadium
's（Ⅰ）Through kneading, shaping, dry, roasting after mixing by 90~98% and 0.5~10% mass percent with metatitanic acid strontium oxide
After obtain finished catalyst.
The preparation method of strontium titanates is not any limitation as, and can such as adopt with the following method：By SrCl2And TiCl4In molar ratio
1.0~1.1 ratio is well mixed, and adds (NH4)2CO3Solution and ammoniacal liquor stir, and the pH value of ammoniacal liquor regulation solution is
9.5~10.5, then it is spray-dried, gained powder is placed in air atmosphere after being dried at a temperature of 120~150 DEG C
1000~1200 DEG C are calcined 4~10 hours, and SrTiO is obtained finally by methods such as air-flow crushing, ball millings3.It is also possible that system
It is standby：By strontium carbonate, titanium dioxide according to SrTiO3Stoichiometric proportion be well mixed, to add and form high dispersive in deionized water
Suspension, is then spray-dried to it, and gained powder is placed in air atmosphere after being dried at a temperature of 120~150 DEG C
1000~1200 DEG C are calcined 4~10 hours, and SrTiO is obtained finally by methods such as air-flow crushing, ball millings3。
It is highly preferred that the lanthanum CeO2-ZrO2 solid solution that weight/mass percentage composition is 0.1~3 can also be added in catalyst,
Catalyst heat endurance 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) prepared according to conventional coprecipitation.
It is highly preferred that containing in catalyst（Ⅰ）92~97%, also metatitanic acid strontium oxide 2~7%.
Acrolein selectivity aoxidizes acrylic acid processed because reaction temperature is basic more than 260 DEG C, and long period is in such height
Under warm reaction condition, the active component molybdenum in catalyst is easy to be lost in because of distillation.B in catalyst of the present invention is preferably lanthanum,
Lanthanum and molybdenum, nickel, copper, antimony etc. can form the crystal phase structure of stabilization, such as Cu2La、LaNi5、LaSb、La5Sb3Deng, be conducive to suppress
Amount of activated component molybdenum loses from catalyst surface because of distillation, and active component molybdenum content is basically unchanged before and after catalyst reaction,
Delay active deterioration rate, catalyst stability is good.Lanthanum and molybdenum, vanadium ratio are appropriate, and B is lanthanum in formula (I), and i is 0.1~3.5
A number, the addition of excessive lanthanum can and vanadium and nickel competition molybdenum, the preferred lanthanum nitrate in lanthanum source of the present invention.Catalyst (I) is mainly constituted
By formula（Ⅱ）Represent：Moa′Vb′Wc′Cud′NifSbgAhLaiOx（Ⅱ）.
Composite multi-metal oxide catalyst of the invention（Ⅰ）Using common preparation method, can such as use down
State step preparation.
Mo, V, W, Cu, Ni, Sb and A will be containedhBiThe compound being related to dissolves and is well mixed, and is formed after being co-precipitated
Slurries, add one or more of the materials such as silica, aluminum oxide, carborundum, and drying, shaping is calcined to obtain catalyst
（Ⅰ）.
Under Oxygen Condition, molybdenum isoreactivity component is not only easy to run off catalyst under the high temperature conditions, and activity compatible is easy
Generation phase in version, activity mutually occurs phase in version causes active selectable to be decreased obviously.Such as active phase VMo3O11It is changed into MoO3,
CoMoO4It is changed into Co3O4, CuMoO4It is changed into MoO3Deng.
Active component molybdenum in catalyst etc. enables and keeps not being lost in, and basic change is little before and after the reaction of molybdenum equal size,
But easily there is phase in version by 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, be not susceptible to phase in version so as to improve catalyst activity and selectivity.
Lanthanum CeO2-ZrO2 solid solution (La of the present inventionxCeyZr1-0.8x-yO2(0<x<1,0<y<1,0<x+y<1) according to routine
Coprecipitation prepare.
The preparation method of catalyst of the present invention, including with coprecipitation prepare catalyst (I), metatitanic acid strontium oxide and/or
Lanthanum CeO2-ZrO2 solid solution, catalyst (I), metatitanic acid strontium oxide is mixed by 90~98% and 0.5~10% mass percent
Close, or add the lanthanum CeO2-ZrO2 solid solution that weight/mass percentage composition is 0.1~3, after mixing through mediating, shaping, dry,
Finished catalyst is obtained after roasting.
Catalyst of the present invention（Ⅰ）And finished catalyst is required for being calcined 3~10h at 300~550 DEG C, compared to not distinguishing
The catalyst of roasting, repeatedly roasting can improve the activity and stability of catalyst.Can be that open roasting can also be closing
Formula is calcined, and calcination atmosphere can be the inert gases such as helium, nitrogen, argon gas.
Catalyst of the present invention（Ⅰ）Each component compound can using each element nitrate, ammonium salt, sulfuric acid
Salt, oxide, hydroxide, chloride, acetate etc..As ammonium molybdate, ammonium metavanadate, magnesium nitrate, ammonium paratungstate, nickel nitrate,
Nickelous carbonate, lanthanum nitrate, ferric nitrate, basic copper carbonate, copper nitrate, antimony oxide, potassium nitrate, titanium oxide, zirconium oxide etc..
After catalyst slurry drying of the present invention, it is usually preferred to using shaping sides such as extrusion molding, granulating and forming, compression moldings
Method processing glomeration, hollow spheres, ellipticity, cylindric, hollow circuit cylinder etc., preferably hollow circuit cylinder or spherical.
Intensity, efflorescence degree in order to improve catalyst of the invention, can add glass fibre, stone in above-mentioned catalyst
One or more in black, ceramic or various whiskers.
Catalyst of the invention can be used directly, and can also be carried on inert carrier and use.Involved inert carrier can
Being the mixture of one or more of aluminum oxide, silica, carborundum etc..
Evaluating catalyst performance index definition is as follows：
Specific embodiment
Composite multi-metal oxide catalyst and preparation method thereof is illustrated with specific embodiment below, and the catalyst exists
Acrolein selectivity oxidation prepares the catalytic performance in acrylic acid, but the scope of the present invention is not limited to these embodiments.Product
The analysis method of composition uses method generally in the art.
Embodiment 1
Under stirring condition, 66.1 grams of 279.3 grams of ammonium molybdates, ammonium metavanadate is taken, be dissolved in 1000ml pure water（Water temperature 65
More than DEG C）, obtain slurries（1）, then take 88.5 grams of ammonium paratungstates, 63.1 grams of copper nitrates, 42.7 grams of nickel nitrates, 13.4 grams of nitric acid
Potassium, 47.7 grams of lanthanum nitrates are dissolved in 1000ml pure water（More than 65 DEG C of water temperature）, it is thoroughly mixed uniformly, obtain slurries（2）.
Then, slurries（1）With slurries（2）Mixing, obtains active component slurries（a）, in active component slurries（a）It is middle to add 8.8 gram two
Silica, 184.5 grams of antimony oxides, 85 DEG C of strong stirrings carry out heat drying after coprecipitation reaction, with 160 DEG C in nitrogen
Heat treatment 3 hours, 500 DEG C are calcined 4 hours, and size-reduced, grinding, sieving process to obtain catalyst（Ⅰ）Powder.The catalyst（Ⅰ）It is main
Constitute and be：Mo14V5W3Cu2.4Ni1.3Sb2.8K0.6La1.3Si1.3Ox（Ⅰ）.
A certain amount of cerous nitrate, lanthanum nitrate, zirconium nitrate are weighed according to stoichiometric proportion, mixed solution is configured to, continuous
In the case of stirring, to mixed solution and dripping ammonia spirit, it is set to carry out coprecipitation reaction, then through suction filtration, 120 DEG C of bakings
Dry, 950 DEG C are calcined 10 hours, and less than 40 μm of fine powder is then ground to form again, and Ce is obtained0.6Zr0.3La0.22O2,
Ce0.5Zr0.4La0.2O2, Ce0.7Zr0.2La0.31O2。
By strontium carbonate, titanium dioxide according to SrTiO3Stoichiometric proportion be well mixed, to add and form high in deionized water
Scattered suspension, is then spray-dried to it, and gained powder is placed in air gas after being dried at a temperature of 120~150 DEG C
1100 DEG C are calcined 10 hours in atmosphere, and SrTiO is obtained finally by ball milling3。
Take catalyst（Ⅰ）95 parts, 4 parts of metatitanic acid strontium oxide, lanthanum CeO2-ZrO2 solid solution Ce0.6Zr0.3La0.22O21 part,
Plus deionized water, in being mediated in kneader, extrusion forming is the hollow columnar particle of 4.5 × 5mm of φ, is dried under the conditions of 120 DEG C,
Roasting obtains catalyst 1 in 6.5 hours at 450 DEG C.
Embodiment 2
Preparation process and primary raw material with the catalyst 1 of embodiment 1 is identical, and catalyst is obtained final product within 4.5 hours through 500 DEG C of roastings
（Ⅰ）.Mainly composition is：Mo14V5W2.5Cu3.2Ni3.4Sb1.6Cs0.5La0.8Si3Ox（Ⅰ）.Take catalyst（Ⅰ）92 parts, strontium titanates oxidation
6 parts of thing, lanthanum CeO2-ZrO2 solid solution Ce0.7Zr0.2La0.31O22 parts, plus deionized water, in being mediated in kneader, extrusion forming is
The hollow columnar particle of 4.5 × 5mm of φ, dries under the conditions of 120 DEG C, and roasting obtains catalyst 2 in 4.5 hours at 500 DEG C.
Embodiment 3
Preparation process and primary raw material with the catalyst 1 of embodiment 1 is identical, and catalyst is obtained final product within 6 hours through 400 DEG C of roastings
（Ⅰ）.Mainly composition is：Mo13V7W5Cu6Ni0.6Sb4.8Cs0.3La3Si1Ox（Ⅰ）.Take catalyst（Ⅰ）97 parts, metatitanic acid strontium oxide
2.5 parts, lanthanum CeO2-ZrO2 solid solution Ce0.5Zr0.4La0.2O20.5 part, plus deionized water is in kneading, extrusion forming in kneader
It is the hollow columnar particle of 4.5 × 5mm of φ, is dried under the conditions of 120 DEG C, roasting obtains catalyst 3 in 4 hours at 550 DEG C.
Embodiment 4
Preparation process and primary raw material with the catalyst 1 of embodiment 1 is identical, and catalyst is obtained final product within 5 hours through 480 DEG C of roastings
（Ⅰ）.Mainly composition is：Mo14V6W4Cu4.8Ni1.3Sb0.8K0.6Fe0.1La2.2Si1.2Ox（Ⅰ）.Take catalyst（Ⅰ）98 parts, strontium titanates
2 parts of oxide, plus deionized water, in being mediated in kneader, extrusion forming is the hollow columnar particle of 4.5 × 5mm of φ, 120 DEG C of bars
Dried under part, roasting obtains catalyst 4 in 5 hours at 500 DEG C.
Comparative example 1
Comparative catalyst 1 is prepared according to the main composition and ratio of embodiment 1, but strontium titanates is not with solid solution, oxide
Form add catalyst, lanthanum cerium zirconium oxide nor adding catalyst in the form of solid solution, oxide, but with coprecipitated
Shallow lake method prepares catalyst, reaction condition with catalyst 1 appreciation condition.The main composition of comparative catalyst 1 is：
Mo14V5W3Cu2.4Ni1.3Sb2.8K0.6La1.52Si1.34Ce0.6Zr0.3Ti0.2Sr0.2Ox（Ⅰ）
Comparative example 2
Comparative catalyst 2 is prepared according to the main composition and ratio of embodiment 1, but strontium titanates is not with solid solution, oxide
Form add catalyst, but catalyst is prepared with coprecipitation method, be added without lanthanum cerium zirconium oxide, reaction condition is with being catalyzed
The appreciation condition of agent 1.The main composition of comparative catalyst 2 is：
Mo14V5W3Cu2.4Ni1.3Sb2.8K0.6La1.3Si1.34Ti0.2Sr0.2Ox（Ⅰ）
Oxidation reaction
Fixed bed single tube reactor internal diameter 25mm, inside sets thermocouple, loads along methacrylaldehyde feedstock direction reactor bed
The above-mentioned catalyst of 50ml or comparative example catalyst, salt bath heating, 250 DEG C of salt temperature.Tube inlet sentences air speed from the reactions above
1700h-1Into the volume % of methacrylaldehyde 10, the volume % of air 14, the volume % of vapor 16, the volume % of nitrogen 60 mixed gas.Urge
The performance of agent is as shown in table 1.Reaction 24 hours.Filling beds hot localised points temperature of the present invention is not higher than 276 DEG C, urges
The indexing of agent bed temperature more rationally, improves purpose product selectivity and yield, acrylic acid total recovery more than 89.0%.It is real
After applying the catalyst reaction 2000h of example 1 and 3, bed hot localised points temperature is respectively 274 DEG C, 276 DEG C, acrolein conversion rate point
Not Wei 99.1% and 99.0%, acrylic acid selectivity is respectively 91.4% and 91.0%, acrylic acid yield 89.7%, 89.6%.Steamed in water
In the case of the volume % of gas intake 16, by the reaction of 2000 hours, catalyst activity component molybdenum etc. was not easily runed off, and living
Property be mutually not susceptible to phase in version, catalyst activity component Stability Analysis of Structures, during acrolein oxidation, reaction bed temperature point
Cloth is more reasonable.Acrylic acid（AA）Yield more than 89.0%, catalyst activity component Stability Analysis of Structures, catalyst has good resisting
Aqueous energy, catalyst performance stabilised.Comparative example catalyst choice is poor, and methacrylaldehyde, acrylic acid yield are low.
The catalyst of embodiment 2 is in 250 DEG C of salt bath heating temperature, air speed 1700h-1, the volume % of methacrylaldehyde 10, the body of air 14
Reacted 24 hours and 2000 hours under conditions of product %, the volume % of vapor 21, the volume % of nitrogen 55, beds focus temperature
Degree is respectively 272 DEG C, 271 DEG C, and acrolein conversion rate is 99.1%, 99.0%, acrylic acid selectivity 90.7%, 90.6%, acrylic acid
Yield 89.1%, 88.9%.Temperature Distribution is more reasonable, catalyst activity component Stability Analysis of Structures, is conducive to catalyst long period steady
Fixed operating.The catalyst of embodiment 2 and 4 is in 250 DEG C of salt bath heating temperature, air speed 1700h-1, the volume % of methacrylaldehyde 10, the body of air 14
Salt temperature to 300 DEG C is adjusted again after stablizing 6 hours under conditions of product %, the volume % of vapor 21, the volume % of nitrogen 55（Stop third
Olefine aldehydr）, by being down to 250 DEG C after 10 hours again, embodiment 2 and 4 is under similarity condition（250 DEG C of salt bath heating temperature, air speed
1700h-1, the volume % of methacrylaldehyde 10, the volume % of air 14, the volume % of vapor 21, the volume % of nitrogen 55）Reaction 24 hours, implements
The bed hot localised points temperature of example 2 and 4 is respectively 270 DEG C, 258 DEG C, and acrolein conversion rate is 98.9%, 98.1%, acrylic acid selection
Property 90.6%, 89.4%, acrylic acid yield 89.1%, 87.9%.By the volume % of vapor 21,300 DEG C of water of salt bath heating temperature
Under conditions of heat treatment, relative to embodiment 4, the catalyst heat endurance of embodiment 2 and good hydrothermal stability, catalyst activity group
Separation structure stabilization, meets catalyst long period steady running.
Table 1 react 24 hours after reaction result
Claims (9)
1. a kind of catalyst for unsaturated aldehyde oxidation, catalyst contains molybdenum, vanadium, tungsten, copper, nickel and antimony element, main composition
By formula M oa′Vb′Wc′Cud′NifSbgAhBiOx(I) represent, wherein：A is selected from least one element in potassium, zinc, caesium；B is
At least one element in selected from magnesium, iron, lanthanum；O is oxygen；A ', b ', c ', d ', f, g, h, i represent each element atomic ratio respectively, its
Middle a ' is a number of 12-14, and b ' is a number of 2-7, and c ' is a number of 1-5, and d ' is a number of 1-6, and f is 0.5-5
A number, g is a number of 0.1-5, and h is a number of 0.1-2.5, and i is a number of 0.1-3.5, and x is by above-mentioned main
The numerical value that the oxygen of each metal oxide in composition is determined；The main composition is with silica, aluminum oxide, carborundum
Kind or it is various be carrier, the catalyst also contain metatitanic acid strontium oxide and lanthanum cerium zirconium sosoloid oxide, the lanthanum cerium zirconium consolidate
The formula of solution oxide is LamCenZr1-0.8m-nO2, wherein, 0<m<1,0<n<1,0<m+n<1, the main composition, strontium titanates
Oxide, lanthanum cerium zirconium sosoloid oxide by 92~97%, 2~7% and 0.1~3% mass percent mixing after through mediate, into
Finished catalyst is obtained after type, drying, roasting, wherein, main composition, metatitanic acid strontium oxide and lanthanum cerium zirconium sosoloid oxide
Mass percent sum is for absolutely.
2. catalyst according to claim 1, it is characterised in that the main composition, metatitanic acid strontium oxide and/or lanthanum cerium
Zirconium oxide solid solution is prepared using coprecipitation.
3. catalyst according to claim 1, it is characterised in that b ' is a number of 2-5 in formula (I).
4. catalyst according to claim 1, it is characterised in that c ' is a number of 1-3.5 in formula (I).
5. catalyst according to claim 1, it is characterised in that d ' is a number of 1.5-4 in formula (I).
6. catalyst according to claim 1, it is characterised in that B is lanthanum in formula (I), is mainly constituted by formula (II) table
Show：Moa′Vb′Wc′Cud′NifSbgAhLaiOx(Ⅱ)。
7. catalyst according to claim 1, it is characterised in that lanthanum source is lanthanum nitrate in formula (I).
8. the catalyst according to any one of claim 3~7, it is characterised in that main composition preparation method includes following step
Suddenly：The compound being related to containing Mo, V, W, Cu, Ni, Sb, A and B is dissolved and is well mixed, slurries are formed after being co-precipitated,
Add silica, aluminum oxide, one or more of silicon carbide species, drying, shaping, be calcined mainly to constitute.
9. catalyst according to claim 8, it is characterised in that prepare the main composition and the finished catalyst
Roasting process is 3~10h of roasting at 400~580 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310585299.7A CN104646016B (en) | 2013-11-19 | 2013-11-19 | Unsaturated aldehyde oxidation catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310585299.7A CN104646016B (en) | 2013-11-19 | 2013-11-19 | Unsaturated aldehyde oxidation catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104646016A CN104646016A (en) | 2015-05-27 |
| CN104646016B true CN104646016B (en) | 2017-06-06 |
Family
ID=53237948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310585299.7A Active CN104646016B (en) | 2013-11-19 | 2013-11-19 | Unsaturated aldehyde oxidation catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104646016B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109718759B (en) * | 2017-10-31 | 2023-11-28 | 中国石油化工股份有限公司 | Molybdenum rare earth metal oxide catalyst, preparation method and application thereof |
| CN110586119A (en) * | 2018-06-12 | 2019-12-20 | 中国石油化工股份有限公司 | Supported catalyst for preparing acrylic acid |
| CN112619645B (en) * | 2019-09-24 | 2023-04-07 | 中国石油化工股份有限公司 | Catalyst for preparing acrylic acid and preparation method and application thereof |
| CN112624917B (en) * | 2020-12-21 | 2023-06-09 | 湖州柏特生物科技有限公司 | Method for producing crotonic acid by catalytic oxidation method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280036A (en) * | 1999-05-13 | 2001-01-17 | 株式会社日本触媒 | Catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid and its use |
| CN1298861A (en) * | 1999-12-08 | 2001-06-13 | 株式会社日本触煤 | Composite oxide catalyst and method for preparing acrylic acid |
| CN1583261A (en) * | 2004-06-11 | 2005-02-23 | 谷育英 | Composite metal oxide for unsaturated aldehyde selective oxidation and preparing method thereof |
| CN102989474A (en) * | 2011-09-08 | 2013-03-27 | 中国石油天然气股份有限公司 | Unsaturated aldehyde oxidation catalyst and preparation method thereof |
| CN102989469A (en) * | 2011-09-08 | 2013-03-27 | 中国石油天然气股份有限公司 | Multi-metal oxide catalyst and preparation method thereof |
| CN102989473A (en) * | 2011-09-08 | 2013-03-27 | 中国石油天然气股份有限公司 | Catalyst for preparing unsaturated acid from unsaturated aldehyde and preparation method thereof |
-
2013
- 2013-11-19 CN CN201310585299.7A patent/CN104646016B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280036A (en) * | 1999-05-13 | 2001-01-17 | 株式会社日本触媒 | Catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid and its use |
| CN1298861A (en) * | 1999-12-08 | 2001-06-13 | 株式会社日本触煤 | Composite oxide catalyst and method for preparing acrylic acid |
| CN1583261A (en) * | 2004-06-11 | 2005-02-23 | 谷育英 | Composite metal oxide for unsaturated aldehyde selective oxidation and preparing method thereof |
| CN102989474A (en) * | 2011-09-08 | 2013-03-27 | 中国石油天然气股份有限公司 | Unsaturated aldehyde oxidation catalyst and preparation method thereof |
| CN102989469A (en) * | 2011-09-08 | 2013-03-27 | 中国石油天然气股份有限公司 | Multi-metal oxide catalyst and preparation method thereof |
| CN102989473A (en) * | 2011-09-08 | 2013-03-27 | 中国石油天然气股份有限公司 | Catalyst for preparing unsaturated acid from unsaturated aldehyde and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104646016A (en) | 2015-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3729704B2 (en) | Catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid, and method for producing unsaturated aldehyde and unsaturated carboxylic acid using the catalyst | |
| JP2013169482A (en) | Catalyst for producing acrylonitrile, method of producing the same, and method of producing acrylonitrile using the same | |
| JP2004509051A (en) | Method for producing multiphase multimetal oxide materials | |
| CN104646016B (en) | Unsaturated aldehyde oxidation catalyst and preparation method thereof | |
| CN103934000A (en) | Acrolein catalyst and preparation method thereof | |
| CN100490973C (en) | Catalyst and Application of Selective Oxidation of Methacrolein to Synthesis of Methacrylic Acid | |
| CN104649892B (en) | Method for selectively oxidizing unsaturated aldehyde | |
| CN103769161A (en) | Acrolein catalyst and preparation method thereof | |
| CN100333834C (en) | Composite metal oxide for unsaturated aldehyde selective oxidation and preparing method thereof | |
| CN104841446B (en) | catalyst for selective oxidation of propylene and preparation method thereof | |
| CN104649894B (en) | Method for preparing acrylic acid by selective oxidation of acrolein | |
| CN104646017B (en) | Catalyst for selective oxidation of acrolein and preparation method thereof | |
| CN104649876B (en) | Preparation method of acrolein | |
| CN104646012B (en) | Propylene selective oxidation catalyst and preparation method thereof | |
| CN104649885B (en) | Method for preparing unsaturated acid from unsaturated aldehyde | |
| CN104646018B (en) | Unsaturated aldehyde selective oxidation catalyst and preparation method thereof | |
| CN104646011B (en) | Low-carbon olefin oxidation catalyst and preparation method thereof | |
| CN104649872B (en) | Method for selectively oxidizing low-carbon olefin | |
| CN104646015B (en) | Propylene oxidation catalyst and preparation method thereof | |
| JP2005058909A (en) | Method for producing catalyst for synthesis of methacrylic acid | |
| CN104649873B (en) | method for selective oxidation of low-carbon olefin | |
| CN104649875B (en) | Propylene selective oxidation method | |
| CN104649893B (en) | A kind of method for preparing unsaturated acid | |
| CN104549350B (en) | Catalyst for preparing acrylic acid and preparation method thereof | |
| CN104646013B (en) | Catalyst for selective oxidation of unsaturated aldehyde and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |