CN104646013A - Catalyst for selective oxidation of unsaturated aldehyde and preparation method thereof - Google Patents
Catalyst for selective oxidation of unsaturated aldehyde and preparation method thereof Download PDFInfo
- Publication number
- CN104646013A CN104646013A CN201310585747.3A CN201310585747A CN104646013A CN 104646013 A CN104646013 A CN 104646013A CN 201310585747 A CN201310585747 A CN 201310585747A CN 104646013 A CN104646013 A CN 104646013A
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- CN
- China
- Prior art keywords
- catalyst
- preparation
- molybdenum
- oxide
- general formula
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 179
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 39
- 230000003647 oxidation Effects 0.000 title claims abstract description 32
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract 4
- 238000002360 preparation method Methods 0.000 title claims description 28
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 51
- 239000010949 copper Substances 0.000 claims abstract description 45
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011733 molybdenum Substances 0.000 claims abstract description 41
- 229910052802 copper Inorganic materials 0.000 claims abstract description 28
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 28
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011777 magnesium Substances 0.000 claims abstract description 26
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 25
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 25
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 239000010936 titanium Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 238000007493 shaping process Methods 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052622 kaolinite Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052714 tellurium Inorganic materials 0.000 claims description 4
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 239000000470 constituent Substances 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 14
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 11
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 9
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 32
- 239000012071 phase Substances 0.000 description 32
- 230000000694 effects Effects 0.000 description 30
- 239000002131 composite material Substances 0.000 description 28
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 22
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 20
- 229910052721 tungsten Inorganic materials 0.000 description 16
- 239000002585 base Substances 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 239000010955 niobium Substances 0.000 description 11
- 239000002184 metal Substances 0.000 description 10
- 229910052758 niobium Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 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
- 239000002253 acid Substances 0.000 description 8
- 239000003377 acid catalyst Substances 0.000 description 8
- 150000001299 aldehydes Chemical class 0.000 description 8
- IKUPISAYGBGQDT-UHFFFAOYSA-N copper;dioxido(dioxo)molybdenum Chemical compound [Cu+2].[O-][Mo]([O-])(=O)=O IKUPISAYGBGQDT-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229910052785 arsenic Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 7
- 239000010937 tungsten Substances 0.000 description 7
- 229910052684 Cerium Inorganic materials 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 229910052715 tantalum Inorganic materials 0.000 description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000009826 distribution Methods 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
- 229910052700 potassium Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 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
- 229910052792 caesium Inorganic materials 0.000 description 4
- 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 4
- 230000008859 change Effects 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 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
- 229910052732 germanium Inorganic materials 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- -1 methyl acrylic aldehyde Chemical compound 0.000 description 4
- 229910052757 nitrogen 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
- 150000003839 salts Chemical class 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-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
- 238000004458 analytical method Methods 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
- 238000001354 calcination Methods 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 230000002779 inactivation Effects 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
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 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
- 239000000843 powder Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-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
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000008901 benefit 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
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001427 coherent effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010438 heat treatment Methods 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
- 230000006872 improvement Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 125000000468 ketone group Chemical group 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
- 238000012423 maintenance Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 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
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000009418 renovation Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 206010013786 Dry skin Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 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
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 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
- 238000000498 ball milling Methods 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
- 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
- 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
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 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
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001934 delay 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
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 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
- 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
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 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
- 230000009257 reactivity 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
- 238000005245 sintering Methods 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical group [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium 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 for selective oxidation of unsaturated aldehyde, which contains molybdenum, vanadium, copper and antimony and mainly comprises the general formula MoaVbCucSbdSreSifMgNhOxAnd (I) the catalyst also contains magnesium-based lanthanum hexaaluminate, wherein the magnesium-based lanthanum hexaaluminate (I) contains molybdenum and vanadium and the magnesium-based lanthanum hexaaluminate are mixed according to the mass percent of 91-98% and 0.5-10%, and then the mixture is kneaded, formed, dried and roasted to obtain the finished catalyst. The catalyst of the invention is used for the selective oxidation reaction of unsaturated aldehyde.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method of unsaturated aldehyde selective oxidation, for methacrylaldehyde or the corresponding unsaturated acids of the oxidation of aldehydes preparation of metering system, be particularly useful for the oxidation of aldehydes acrylic acid processed of catalyzing propone.
Background technology
The reaction unit mainly many reaction tubes of industrial methacrylaldehyde or the corresponding unsaturated acids of the oxidation of aldehydes preparation of metering system, ensureing that catalyst is not sintered, under the prerequisite of long service life, improve selective and object product yield as far as possible, conservation, even if if feed stock conversion, methacrylaldehyde acrylic acid yield improve 0.1 ~ 0.5 percentage point, the amount of the product obtained increases with the level of hundreds of ~ thousands of tons of, and its economic benefit is also very considerable.
About propylene fraction oxidation acrolein, acrylic acid catalyst mainly molybdenum system multicomponent catalyst.Preparing the acrylic acid reaction of methacrylaldehyde due to Propylene Selectivity oxidation is strong exothermal reaction, so pass into the large steam of specific heat in course of reaction, effectively to remove reaction heat, but the easy losses under the washing away of the air-flows such as steam such as the active component molybdenum in catalyst.And under the high temperature conditions, in catalyst, part active component molybdenum loses from catalyst surface because of distillation.The loss of active component molybdenum causes reducing the activity of catalyst, selective, intensity and service life, and molybdenum is in the deposition in reaction system downstream, blocks the long-term operation of pipeline influential system.
In addition, the active component molybdenum in catalyst etc. i.e. enable maintenance is not run off, and before and after the reaction of molybdenum equal size, basic change is little, but is through long-term operation activity compatible and easily phase in version occurs.Key component in catalyst comprises Fe
2(MoO
4)
3, α-Bi
2(MoO
4)
3, CoMoO
4and NiMoO
4, wherein α-Bi
2(MoO
4)
3be Active sites, play selective oxidation effect; Fe
2(MoO
4)
3play redox facilitation; CoMoO
4and NiMoO
4play Stability Analysis of Structures effect.But, adopt the catalyst prepared of coprecipitation method due to component many, process is complicated, and catalyst stabilization differs, although initial activity is very high, inactivation is fast.What cause many components Mo-Bi-Co-Fe-O catalyst and Mo-V-O catalysqt deactivation and stability to decline is a lot of because have, comprising because of locally abnormal high temperature (focus) cause the sublimation of Mo component and irreversible crystalline phase change etc.These factors all can cause the change of specificity of catalyst, cause the reduction of catalyst activity and shorten service life of catalyst.By carrying out phenetic analysis to decaying catalyst, find Fe
2(MoO
4)
3be reduced into FeMoO
4, and α-Bi
2(MoO
4)
3change γ-Bi into
2moO
6.
Solve the problem, the patent related to is many, such as, for suppressing the loss of molybdenum, CN1583261 discloses a kind of O composite metallic oxide catalyst for carrying out selective oxidation reaction in the gas phase containing the gas of unsaturated aldehyde and a kind of gas of molecule-containing keto, and its catalyst consists of: [Mo
av
bcu
cx
d] Y
m[Sb
ez
1 fz
2 g]
no
xwherein Mo is molybdenum, and V is vanadium, and Cu is copper, and Sb is antimony, and X is a kind of element being at least selected from tungsten and niobium, and Y is a kind of element being at least selected from titanium, antimony, Z
1a kind of element of at least chosen from Fe and nickel, Z
2it is a kind of element being at least selected from silicon, aluminium, alkali and alkaline earth metal ions, a, b, c, d, e, f, g and x represent the atomic ratio number of its element, when a=12 is benchmark, b is a number of 1 to 6, c is a number of 0.5 to 4, and d is a number of 0.05 to 4, and e is a number of 0.1 to 30, f is a number of 0 to 25, and g is a number of 0.01 to 20; X is by the number met 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, use ammonium metavanadate and copper nitrate respectively, and with Low Valent Vanadium oxide and/or at a low price Cu oxide part replace catalyst that raw material that ammonium metavanadate and/or copper nitrate make vanadium metal and copper obtains or except above-mentioned raw materials except, using sb oxide and/or low price tin-oxide obtain at a low price catalyst to demonstrate has a strengthened peak (vanadium-molybdenum reactive compound is peculiar) at d=4.00 and has the V of a remitted its fury at d=4.38_
2o
5specific peak.Like this, catalyst obtained above has the catalytic activity of raising, and long-term performance can go out stability.Similar also has patent document 1: Japanese Unexamined Patent Publication 2002-233757 publication, patent document 2: Japanese Unexamined Patent Publication 8-299797 publication, patent document 3: Japanese Unexamined Patent Publication 9-194213 publication, patent document 4: Japanese Unexamined Patent Application Publication 2004-504288 publication; CN102066000A.
For improving activity, the selective and catalyst life of catalyst, CN200980112659.3 discloses a kind of coated catalysts comprising following component: (a) carrier, b () comprises molybdenum oxide or forms the ground floor of precursor compound of molybdenum oxide, (c) comprises the second layer of the poly-metal deoxide containing molybdenum and other metal of at least one.The molybdenum oxide of preferred ground floor is MoO
3, the poly-metal deoxide of the second layer is the poly-metal deoxide that general formula I I represents: Mo
12bi
acr
bx
1 cfe
dx
2 ex
3 fo
y.This catalyst is the application type catalyst comprising carrier.Goal of the invention suppresses heterogeneously catalysed partial gas phase oxidation methacrylaldehyde to be acrylic acid coated catalysts inactivation, has the inactivation performance of improvement.This invention is not clearly recorded catalyst and is used for catalyzing propone oxidation acrolein, acrylic acid reactivity worth evaluating data, such as conversion ratio, selective, yield etc.CN87103192 discloses a kind of method of producing composite oxide catalysts, wherein comprise coherent element source compound to mix in Aquo System by the production method of the Mo-Bi composite oxide catalysts of following chemical formulation and form compound and this compound is heat-treated, adopt a kind of compound of the waltherite compound of (a) Bi and Na or (b) Bi, Na and X or (c) Bi and X as Bi source, in this compound at least containing required Na and/or X of 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, and as a=12, b=0.5-7, c=0-10, d=0-10, c+d=1-10, e=0.05-3, f=0.01-1, g=0-1, h=0.04-0.4, i=0-3, j=0-48, k is a number meeting other element oxide state.Solve Bi can in composite oxide catalysts homodisperse problem.Containing α-Bi in catalyst
2(MoO
4)
3, MoO
3fe
2(MoO
4)
3with β-CoMoO
4, y-Bi
2moO
6and γ-Bi
2moO
6.CN101690900A discloses a kind of preparation method preparing methacrylaldehyde and acrylic acid catalyst, and catalyst supports thing by active component and inert alumina carrier forms; The main component of active component, is selected from Mo, Bi, Co and/or Ni and Fe, also comprises the trace elements such as K, Na, Rb, Cs, Mg, Ca, Zn, B, P, W; Wherein the following statement formula of active component represents: Mo
abi
bco
cni
dfe
ex
fy
gz
ho
iin formula, X represents at least one of K, Na, Rb and Cs, and Y represents at least one be selected from B, P and W, and Z represents at least one be selected from Mg, Ca, Zn.The active component ratio be supported on carrier accounts for the 5-70% of overall catalyst weight; Active component is uneven distribution, CoMoO
4, NiMoO
4aluminate Deng divalent metal is positioned at the kernel of catalyst activity component; Fe
2(MoO
4)
3and the MoO of free state
3invest the skin of kernel; And the outermost layer of active component is bismuth molybdate, form the state of core-shell structure copolymer layer distributed.In active component, divalence molybdate is mainly beta phase structure, and α phase structure content in active component is very low or do not exist.Catalyst has high activity and high stability.CN1280036 mono-kind produces the catalyst of unsaturated aldehyde and unsaturated carboxylic acid, described production is by making at least one be selected from propylene, isobutene, the compound of the tert-butyl alcohol and methyl tertiary butyl ether(MTBE) and oxygen molecule or the gas containing oxygen molecule carry out vapour-phase oxidation and realize, it is characterized in that this catalyst is a kind of combined oxidation compositions, contain: (A) is containing molybdenum, bismuth and iron are as the composite oxides of key component, it itself is the known catalyst reacted for described vapor phase catalytic oxidation, (B) containing cerium and the zirconium composite oxides as key component.Catalyst has long catalytic life and makes running steady in a long-term become possibility.Wherein component (B) is the composite oxides represented with following general formula (2): Ce
pzr
qf
ro
y.The zirconia of high degree of dispersion inhibits the gathering of cerium oxide, to keep the latter to the promotion functions absorbing and discharge oxygen significantly in course of reaction, thus accelerates the oxidation reaction of isobutene, therefore improves catalytic activity.In addition, the irreversible activity that further suppress component (A) composite oxides caused because of over reduction in time reduces (i.e. the stability raising of composite oxides), thus catalytic life is extended.This catalytic activity that improve and the catalytic life extended inhibit reaction temperature to raise in time, thus reduce the distillation of molybdenum at hot spot.This catalyst is used for isobutylene oxidation.
CN102489309A discloses a kind of catalyst preparing for the production of methacrylaldehyde and renovation process.Catalyst is the composite oxides with following atomic ratio: Mo: Bi: Co: Ni: Fe=10-14: 1.2-2.0: 4.8-5.6: 2-3: 1-2; This catalyst has the pore size distribution of comparatively concentrating, moderate total pore volume, wherein the mesopore of about 5-10nm accounts for more than 70% of total pore size distribution, form short and thick pore passage structure, this feature gives catalyst stronger anti-carbon deposition ability, catalyst surface is easy-sintering not, can service life of extending catalyst.And by renovation process provided by the invention, decaying catalyst carries out 1-3 days calcination processing in an oxidizing atmosphere, and catalyst activity is suitable with fresh catalyst.CN87103192 produces the method for Mo-Bi-Na composite oxide catalysts product, the method comprises mixes coherent element source compound and form compound, then heat-treats, and using at least solid solution, the basic bismuth carbonate of the required Na of part is as Bi source compound.The activity of catalyst is able to great improvement by means of Bi and Na imports the catalyst of specific water-insoluble compound formation.
CN1109803 relates to multimetal oxide compositions, and they have two phase structure and comprise molybdenum, hydrogen, one or more element phosphor, arsenic, boron, germanium and silicon; And relate to described composition and prepared the purposes in methacrylic acid by catalytic gas phase oxidation, improve activity and selectivity.CN1109802 discloses a kind of multimetal oxide compositions, and they have two phase structure and comprise molybdenum, hydrogen, one or more element phosphor, arsenic, boron, germanium and silicon and copper, improves base acrylic acid activity and selectivity.CN1298861A adopts the composite oxides adding magnesium, aluminium and silicon.CN1321110A is then respectively using antimony oxide and antimony acetate as the antimony source of active composite metal oxide.Under solving high-load condition, catalytic mechanical intensity is good, active high problem.CN200410048021.7 discloses a kind of O composite metallic oxide catalyst, and catalyst is by 1. molybdenum, vanadium, copper main active component and 2. requisite at least by stable component and the 3. composite oxides that form of nickel, iron, silicon, aluminium, alkali metal, alkaline-earth metal of antimony and titanium.2. and be 3. wherein can composite oxides that within the scope of 120 DEG C to 900 DEG C prepared by roasting.This catalyst shows the permanent stability under high activity and good selectivity.CN1121441 discloses a kind of for by methacrylaldehyde or carry out oxidation reaction containing the gas of acrolein gas and a kind of molecule-containing keto in vapour phase and produce acrylic acid catalyst, this catalyst comprises (A) a kind of composite oxides, there is molybdenum and vanadium as base stock, and be suitable for by vapor phase catalytic oxidation methacrylaldehyde to produce acrylic acid, (B) solid peracid, its acid strength (Ho) is not more than-11.93 (Ho≤-11.93).This invention adopts molybdenum vanadium type composite oxides to combine with the solid acid that a kind of acid strength is no more than-11.93, improves the low temperature high activity of catalyst.CN200510059468.9 discloses a kind of acrylic acid catalyst for producing, it is characterized in that, the oxide of the metallic element composition represented at following formula M oaVbWcCudOx (1) and/or composite oxides are must in the acrylic acid catalyst for producing of catalyst component, need to control the face side that tungsten is this catalyst partially, 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) preparation method of composite oxide coating: be dispersed in water/organic phase mixed system by the water-soluble metal salt containing Mo, V, W, Cu, Sb composition in 30-100 DEG C; Organic solvent and water weight ratio is kept to be 5 ~ 50%; Reaction generates composite oxides presoma slurries; Catalyst activity component is obtained again through distillation, oven dry, roasting; B) the main component of above-mentioned active component, be selected from Mo, V, Cu, W, Sb wherein one or more; Wherein active component following formula represents: Mo
av
bcu
cw
dsb
eo
fthis catalyst adopts the mixed system preparation of water and lower alcohol, and catalyst has higher specific area and special microstructure, has comparatively high-ratio surface and difficult drop-off, and bearing capacity can reach 50% and more than, solve shorter problem in application type catalyst service life.
CN1647854 discloses a kind of catalyst of selectively oxidizing methyl acrylic aldehyde to synthesize methyl propenoic acid, and the composition general formula of this catalyst is: x (Mo
12p
ak
bsb
ccu
das
ea
fd
gq
ho
imo
j)/yZ, Z is carrier dilution thermal conducting agent; Mo, P, K, Sb, Cu and As are respectively molybdenum, phosphorus, potassium, antimony, copper and arsenic; A represents at least one element in tungsten W, vanadium V, niobium Nb, iron Fe and plumbous Pb; D represents at least one element in boron, gallium Ga, indium In, germanium Ge and silicon Si; Q represents at least one element in rubidium Rb, caesium Cs and thallium Tl, and this invention improves the activity and selectivity of catalyst on the one hand by adding Sb, Cu and As; On the other hand by adding MoO
3improve the heat endurance of catalyst, heat conductivility and mechanical strength with carrier heat conduction diluent, effectively inhibit activities component heteropolyacid salt decomposition and reduce beds hot(test)-spot temperature, avoid the loss of Mo and As, extending catalyst service life.
CN1109800 discloses a kind of polymetal oxide materials: in formula, A is Mo
12v
ax
b 1x
c 2x
d 3x
e 4x
f 5x
g 6o
x(coexisting phase), its part B comprises the crystallite (giving the firsthand information about X-ray diffraction fingerprint in round parentheses) of the X-ray diffraction pattern with the following copper molybdate of at least one: Cu
3(MoO
4)
2(OH)
2(lindgernite, the card index 36-405 of JCPDS-ICDD index (1991)), Cu
4mo
6o
20(people such as A.Moini, Inorg.Chem.25(21) (1986), 3782-3785), Cu
4mo
5o
17(the card index 39-181 of JCPDS-ICDD index (1991)), etc.CN1462211 relates to a kind of method preparing multiple-phase multi-metal oxide materials containing Mo, V, Cu and other optional element.According to this invention, at least one phase is pre-formed independently, and is dispersed in the precursor material of the plastically deformable of another phase.Then this mixture carries out drying and calcining.Polymetal oxide materials is suitable as at catalytic gas phase oxidation organic compound, particularly acrolein oxidation is being become the active material of catalyst used in acrylic acid.[A] p [B] q [C] r (I), the phase A in multimetal oxide compositions, B and C can be unbodied and/or crystallizations.Phase B is advantageously made up of the crystallite of oxometallate, or comprises there is X-ray diffraction pattern and and then the crystal structure class α-CuMo of oxometallate crystallite copper molybdate of crystal structure types of the following copper molybdate of at least one
4[the registration card 22-242 of JCPDS-ICDD card index, (1991)], Cu
6mo
5o
18[the registration card 40-865 of JCPCS-ICDD card index, (1991)], Cu
4-xmo
3o
12, wherein x=0-0.25 [registration card 24-56 and 26-547 of JCPCS-ICDD card index, (1991)], etc.This catalyst is selective in order to improve.
CN1295499 discloses polymetal oxide materials [A] p [B] q [C] r (I) of a kind of formula (I), with containing molybdenum, vanadium, copper and antimony and one or more other metals specific and the polymetal oxide materials with multicomponent structure prepares acrylic acid catalyst as with the gas phase catalytic oxidation reaction of methacrylaldehyde.In formula, A is Mo
12v
ax
1bX
2 cx
3 dx
4 ex
5 fx
6 go
x, B is X
1 7cu
hh
io
y, C is X
1 8sb
jh
ko
z, X
1for W, Nb, Ta, Cr and/or Ce.Co-catalyst phase B is made up of the crystallite of these copper molybdate or contains such copper molybdate crystallite: α-CuMoO
4[the reference diffraction pattern in the index card 22-242 of JCPDS-ICDD retrieval 1991], Cu
6mo
5o
18[the reference diffraction pattern in the index card 40-865 of JCPDS-ICDD retrieval 1991], Cu
4-xmo
3o
12wherein, x is 0-0.25 [the reference diffraction pattern in index card 24-56 and 26-547 of JCPDS-ICDD retrieval 1991], etc.Region C can have metaantimmonic acid copper Cu
9sb
4o
19the crystallite of structure or Cu
4sbO
4.5the crystallite of structure.CN1093950 discloses the composition of one kind of multiple metal oxides, comprise Mo, V, W, Cu, the Ni of the oxidised form as basis, its prerequisite there is following ratio between each elemental composition: 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.X
1one or more alkali metal; X
2one or more alkaline-earth metal; X
3cr, Mn, Ce and/or Nb; X
4sb and/or Bi; X
5si, Al, Ti and/or Zr.CN1387945 relates to the oxo metallide of the HT copper molybdate structure type being selected from the element in element W, V, Nb and Ta containing Cu, Mo and at least one, its preparation method, and they also contain the application had in the composite metal oxide material of heterogeneous structure of one or more elements in elemental tungsten, niobium, tantalum, chromium and cerium in preparation containing molybdenum, vanadium, copper.The poly-metal deoxide that CN1394812 uses in the catalyst of the catalytic vapor phase oxidation reaction for organic compound, said poly-metal deoxide contains at least one in Mo, V and element W, Nb, Ti, Zr, Hf, Ta, Cr, Si and Ge, and has special Three-dimensional atom arrangement.CN1500770 contains molybdenum, vanadium, the composite metal oxide material that have heterogeneous structure of copper also containing one or more elements in elemental tungsten, niobium, tantalum, chromium and cerium, they are by the application in catalytic gas phase oxidation of acrolein acrylic acid, and are selected from the oxo metallide of the HT copper molybdate structure type of the element in element W, V, Nb and Ta containing Cu, Mo and at least one.
In addition, under the high temperature conditions, in catalyst, part active component molybdenum loses from catalyst surface because of distillation.The mixed airflows such as methacrylaldehyde, air (oxygen), nitrogen and steam wash away the loss of active component that also can make in catalyst.For suppressing the loss of molybdenum distillation to cause active decay, CN1121504, by mixing copper component and having the zirconium of specified particle diameter and specific area and/or titanium and/or cerium, can suppress dissipation effect and the over reduction of molybdenum composition.Catalyst comprises by following formula (I) MO
av
bw
ccu
dx
ey
f(I) oxide of the metallic element composition represented or composite oxides.CN1445020 adds the effect that a small amount of tellurium plays stable free molybdenum trioxide and copper molybdate crystal structure, and sublimation and the over reduction of molybdenum suppress to some extent; CN1583261 is with molybdenum, vanadium, copper, tungsten and/or niobium for key component, and the composite oxides formed with other element or its hopcalite form the loss that catalyst suppresses molybdenum.
Therefore, the catalyst agent active component molybdenum etc. providing methacrylaldehyde or MAL selective oxidation to produce corresponding unsaturated acids is needed not easily to run off, and not easily there is phase in version in active phase, make methacrylaldehyde long period stably selective oxidation production acrylic acid, in acrolein oxidation process, react under low temperature, high-load condition, temperature of reactor distribution is more reasonable, and improve the selective and yield of object product as far as possible, to obtain larger economic benefit.
Summary of the invention
The object of this invention is to provide catalyst and the preparation method of unsaturated aldehyde selective oxidation, produce corresponding unsaturated acids for methacrylaldehyde or MAL selective oxidation, be particularly useful for acrolein selectivity oxidation and prepare acrylic acid.
The present invention relates to a kind of multi-metal-oxide catalyst, be mainly used in methacrylaldehyde or MAL selective oxidation produces corresponding unsaturated acids, catalyst contains molybdenum, vanadium, copper and antimony element, mainly forms by formula M o
av
bcu
csb
dsr
esi
fm
gn
ho
x(I) represent, catalyst, also containing magnesium base lanthanum hexaaluminate, obtains finished catalyst by after 91 ~ 98% and 0.5 ~ 10% mass percent mixing containing molybdenum, (I) of vanadium and magnesium base lanthanum hexaaluminate after kneading, shaping, dry, roasting.
Wherein: Mo is molybdenum, V is alum, and Cu is copper, and Sb is antimony, and Sr is strontium, and Si is silicon, and silicon is the carrier added, and M is at least one element be selected from zinc, calcium, lanthanum, phosphorus, boron; N is at least one element be selected from tellurium, zirconium, titanium; O is oxygen; A, b, c, d, e, f, g, h represent each Elements Atom ratio respectively, and wherein a=12, b are numbers of 2 ~ 7, preferably 2 ~ 6; C is a number of 0.5 ~ 5, preferably 0.5 ~ 4; D is a number of 0.5 ~ 5, preferably 1.0 ~ 4; E is a number of 0.1 ~ 2.5, and f is a number of 0.5 ~ 40, preferably 0.5 ~ 25; G is a number of 0.1 ~ 4, and h is a number of 0.05 ~ 3, and x is the numerical value determined by the oxygen of each oxide.
More preferably, containing catalyst (I) 92 ~ 97% in catalyst of the present invention, containing magnesium base lanthanum hexaaluminate 1 ~ 8%.
The preferred lanthanum of M in catalyst Formula of the present invention (I), lanthanum and antimony, copper etc. can form stable crystal phase structure, as LaSb, La
5sb
3, Cu
2la, Cu
5la etc., thus suppress part active component molybdenum to lose from catalyst surface because of distillation, active component molybdenum not easily runs off, and delays active deterioration rate, catalyst activity and good stability.Lanthanum and molybdenum, vanadium ratio are suitable, and in general formula (I), h is a number of 0.5 ~ 3.The preferred lanthanum nitrate in lanthanum source of the present invention, the preferred sodium stannate of Xi Yuan, stannous chloride.Catalyst mainly forms and is represented by general formula (II): Mo
av
bcu
csb
dsr
esi
fla
gn
ho
x(II).
Magnesium base lanthanum hexaaluminate oxide of the present invention coprecipitation preparation conveniently.Prepare as adopted following method: by magnesium nitrate, lanthanum nitrate and aluminium hydroxide according to LaMgAl
11o
19stoichiometric proportion mix, add deionized water and stir, then spraying dry, gained powder after 160 DEG C of dryings through 1000 ~ 1500 DEG C of roastings 3 ~ 12 hours, then by pulverize or the method such as ball milling obtains the magnesium base lanthanum hexaaluminate LaMgAl of particle diameter below 20 μm
11o
19.
The preparation method of catalyst of the present invention, comprise with coprecipitation Kaolinite Preparation of Catalyst (I), magnesium base lanthanum hexaaluminate, by catalyst (I), magnesium base lanthanum hexaaluminate by after 88 ~ 96% and 0.5 ~ 10% mass percent mixing through mediating, obtain finished catalyst after shaping, dry, roasting.
Under Oxygen Condition, catalyst under the high temperature conditions molybdenum isoreactivity component not only runs off, and activity compatible easily phase in version occurs, and activity mutually phase in version occurs thus causes active selectable obviously to decline.As active phase VMo
3o
11change MoO into
3, CoMoO
4change Co into
3o
4, CuMoO
4change MoO into
3deng.
Active component molybdenum in catalyst etc. i.e. enable maintenance is not run off, and before and after the reaction of molybdenum equal size, basic change is little, but is through long-term operation activity compatible and easily phase in version occurs.Magnesium base lanthanum hexaaluminate adds in catalyst by the present invention, makes active phase more stable, not easily phase in version occurs thus improves catalyst activity and selectivity.
Composite multi-metal oxide catalyst of the present invention (I) adopts common preparation method, prepares as adopted following step.
By M in the compound containing Mo, V, Cu, Sb, Sr and general formula (I)
gn
heach elemental constituent compound that part relates to dissolves in proportion and mixes, and forms slurries, add one or more in silica, aluminium oxide or carborundum in slurry production process after carrying out co-precipitation, and dry, shaping, roasting obtains catalyst (I) powder.
Catalyst of the present invention (I) powder and finished catalyst all need roasting 3 ~ 10h at 400 ~ 550 DEG C, and compare the catalyst of not roasting respectively, repeatedly roasting can improve activity and the stability of catalyst.Can be open roasting also can be enclosed roasting, calcination atmosphere can be the inert gases such as helium, nitrogen, argon gas.
The compound of each component of catalyst of the present invention can use the nitrate, ammonium salt, sulfate, oxide, hydroxide, chloride, acetate etc. of each element.As ammonium molybdate, ammonium metavanadate, copper nitrate, Schweinfurt green, antimony oxide, strontium nitrate, zinc nitrate, calcium nitrate, lanthanum nitrate, phosphoric acid, boric acid, tellurium oxide, zirconia, titanium oxide etc.
After catalyst slurry of the present invention is dried, the forming methods such as extrusion molding, granulating and forming, compression molding are usually preferably adopted to be processed into spherical, hollow spheres, ellipticity, cylindric, hollow circuit cylinder etc., preferably hollow circuit cylinder or spherical.
Catalyst of the present invention can directly use, and also can be carried on inert carrier and use.Involved inert carrier can be the mixture of one or more of aluminium oxide, silica, carborundum etc.
Evaluating catalyst performance index definition is as follows:
Detailed description of the invention
With specific embodiment, composite multi-metal oxide catalyst and preparation method thereof is described below, and this catalyst is oxidized the catalytic performance prepared in acrylic acid at acrolein selectivity, but scope of the present invention is not limited to these embodiments.The analytical method of product composition adopts this area universal method.
Embodiment 1
The preparation of catalyst 1
1. Kaolinite Preparation of Catalyst (I)
Under agitation, get 180.1 grams of ammonium molybdates, ammonium metavanadate 19.9 grams, be dissolved in (water temperature more than 65 DEG C) in 1000ml pure water, obtain slurries (1), then get 98.9 grams of copper nitrates, 26.7 grams of strontium nitrates, 2.5 grams of zinc nitrates are dissolved in (water temperature more than 65 DEG C) in 1000ml pure water, fully be uniformly mixed, obtain slurries (2).Then, slurries (1) mix with slurries (2), obtain slurries (3), then add 1.4 grams of titanium dioxide, 64.4 grams of antimony oxides, obtain active component slurries (a).4.6 grams of silica and 3.1 grams of graphite are added in active component slurries (a), 80 DEG C of strong stirrings carry out heat drying after coprecipitation reaction, with 160 DEG C of heat treatments 3 hours in nitrogen, then extruded through banded extruder is the hollow columnar particle of φ 4.5 × 5mm, dry rear 460 DEG C of roastings 5 hours for 110 DEG C, obtained catalyst (I), this catalyst (I) mainly consist of: Mo
12v
2cu
5sb
1.3sr
1.2si
0.9zn
0.1ti
0.2o
x.
Get catalyst (I) 92 part, magnesium base lanthanum hexaaluminate 8 parts, adds deionized water and mediates in kneader, and extruded is the hollow columnar particle of φ 4.5 × 5mm, and dry under 120 DEG C of conditions, at 550 DEG C, roasting obtains catalyst 1 in 3.5 hours.
Embodiment 2
The preparation of catalyst 2
With the preparation process of embodiment 1 catalyst 1 and primary raw material identical, within 4 hours, namely obtain catalyst (I) through 480 DEG C of roastings.Catalyst (I) mainly consist of: Mo
12v
6cu
0.6sb
0.5sr
1.9si
2.3la
3zr
0.3ti
0.2o
x,
Get catalyst (I) 97 part, magnesium base lanthanum hexaaluminate 3 parts, adds deionized water and mediates in kneader, and extruded is the hollow columnar particle of φ 4.5 × 5mm, and dry under 120 DEG C of conditions, at 500 DEG C, roasting obtains catalyst 2 in 3.5 hours.
Embodiment 3
With the preparation process of embodiment 1 catalyst 1 and primary raw material identical, within 4 hours, namely obtain catalyst (I) through 500 DEG C of roastings.Catalyst (I) mainly consist of: Mo
12v
4cu
3.5sb
3.5sr
0.1si
1.1la
1.0zr
0.2o
x, get catalyst (I) 94 part, magnesium base lanthanum hexaaluminate 6 parts, adds deionized water and mediates in kneader, and extruded is the hollow columnar particle of φ 4.5 × 5mm, and dry under 120 DEG C of conditions, at 500 DEG C, roasting obtains catalyst 3 in 4 hours.
Embodiment 4
With the preparation process of embodiment 2 catalyst 2 and primary raw material identical, within 7 hours, namely obtain catalyst (I) 370 DEG C of roastings.Catalyst (I) mainly consist of: Mo
12v
7cu
1.8sb
5sr
2.4si
1.2b
0.6la
2te
0.1o
x,
Get catalyst (I) 98 part, magnesium base lanthanum hexaaluminate 2 parts, adds deionized water and mediates in kneader, and extruded is the hollow columnar particle of φ 4.5 × 5mm, and dry under 120 DEG C of conditions, at 500 DEG C, roasting obtains catalyst 4 in 4 hours.
Comparative example 1
Main composition and ratio according to embodiment 1 prepares comparative catalyst 1, but magnesium base lanthanum hexaaluminate is not add catalyst with the form of solid solution, oxide, but with coprecipitation method Kaolinite Preparation of Catalyst, reaction condition is with the appreciation condition of catalyst 1.Comparative catalyst 1 mainly consists of:
Mo
12V
2Cu
5Sb
1.3Sr
1.2Si
0.9Zn
0.1Ti
0.2La
0.3Mg
0.3Al
3.3O
x。
Oxidation reaction
Fixed bed single tube reactor internal diameter 25mm, inside establishes thermocouple, loads the above-mentioned catalyst of 45ml or comparative example catalyst, salt bath heating, salt temperature 245 DEG C along feedstock direction reactor bed.From above-mentioned reaction tube porch with air speed 1150h
-1the mist of methacrylaldehyde 9 volume %, air 14 volume %, steam 16 volume %, nitrogen 61 volume %.The performance of catalyst is as shown in table 1.React 24 hours, load beds hot localised points temperature of the present invention not higher than 267 DEG C, reaction bed temperature calibration is more reasonable, improve object selectivity of product and yield, acrylic acid yield more than 88.7%, after the catalyst reaction 2000h of embodiment 1 and 2, bed hot(test)-spot temperature is respectively 263 DEG C DEG C, 266 DEG C, acrolein conversion rate is respectively 99.2% and 99.1%, and acrylic acid (AA) is selective is respectively 91.1% and 91.2%, acrylic acid yield 89.5%, 89.3%.When steam intake 15 volume %, through the reaction of 2000 hours, catalyst activity component molybdenum etc. not easily runs off, and not easily there is phase in version in active phase, catalyst activity component structure is stablized, in acrolein oxidation process, reaction bed temperature distribution is more reasonable, makes the steady running of catalyst long period.Acrylic acid (AA) yield more than 88.7%, catalyst activity component structure is stablized, and catalyst has good water repelling property, catalyst performance stabilised.Comparative example catalyst choice is poor, and methacrylaldehyde, acrylic acid yield are low.
Table 1 reacts 24 hours post-evaluation results
Claims (8)
1. for a catalyst for unsaturated aldehyde selective oxidation, catalyst contains molybdenum, vanadium, copper and antimony element, mainly forms by formula M o
av
bcu
csb
dsr
esi
fm
gn
ho
x(I) represent, catalyst is also containing magnesium base lanthanum hexaaluminate, containing molybdenum, (I) of vanadium and magnesium base lanthanum hexaaluminate by after 91 ~ 98% and 0.5 ~ 10% mass percent mixing through mediating, obtain finished catalyst after shaping, dry, roasting, wherein: silicon is the carrier added, M is at least one element be selected from zinc, calcium, lanthanum, phosphorus, boron; N is at least one element be selected from tellurium, zirconium, titanium; O is oxygen; A, b, c, d, e, f, g, h represent each Elements Atom ratio respectively, wherein a=12, b is a number of 2 ~ 7, c is a number of 0.5 ~ 5, and d is a number of 0.5 ~ 5, and e is a number of 0.1 ~ 2.5, f is a number of 0.5 ~ 40, g is a number of 0.1 ~ 4, and h is a number of 0.05 ~ 3, and x is the numerical value determined by the oxygen of each oxide.
2. catalyst according to claim 1, is characterized in that containing catalyst (I) 92 ~ 97%, containing magnesium base lanthanum hexaaluminate 1 ~ 8%.
3. the preparation method of catalyst according to claim 1, it is characterized in that comprising with coprecipitation Kaolinite Preparation of Catalyst (I), magnesium base lanthanum hexaaluminate, by catalyst (I), magnesium base lanthanum hexaaluminate by after 91 ~ 98% and 0.5 ~ 10% mass percent mixing through mediating, obtain finished catalyst after shaping, dry, roasting.
4. catalyst according to claim 1, it is characterized in that in general formula (I), b is a number of 2 ~ 6, c is a number of 0.5 ~ 4.
5. catalyst according to claim 1, it is characterized in that in general formula (I), d is a number of 1.0 ~ 4, f is a number of 1 ~ 25.
6. catalyst according to claim 1, it is characterized in that in general formula (I), M is lanthanum, h is a number of 0.5 ~ 3, and catalyst (I) mainly composition is represented by general formula (II): Mo
av
bcu
csb
dsr
esi
fla
gn
ho
x(II).
7. the catalyst according to any one of claim 4 ~ 6, is characterized in that the preparation of catalyst (I) comprises the steps: M in the compound containing Mo, V, Cu, Sb, Sr and general formula (I)
gn
heach elemental constituent compound that part relates to dissolves in proportion and mixes, and form slurries after carrying out co-precipitation, add one or more in silica, aluminium oxide or carborundum etc. in slurry production process, drying, shaping, roasting obtains catalyst (I).
8. the preparation method of catalyst according to claim 3, is characterized in that catalyst (I) and finished catalyst roasting 3 ~ 10h at 400 ~ 550 DEG C.
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| EP1074538A2 (en) * | 1999-08-04 | 2001-02-07 | Nippon Shokubai Co., Ltd. | Process for producing acrolein and acrylic acid |
| CN102247863A (en) * | 2010-05-18 | 2011-11-23 | 中国石油天然气股份有限公司 | Three-layer multi-metal oxide catalyst and preparation method thereof |
| CN102247862A (en) * | 2010-05-18 | 2011-11-23 | 中国石油天然气股份有限公司 | Multilayer composite 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 |
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2013
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| EP1074538A2 (en) * | 1999-08-04 | 2001-02-07 | Nippon Shokubai Co., Ltd. | Process for producing acrolein and acrylic acid |
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| CN102247862A (en) * | 2010-05-18 | 2011-11-23 | 中国石油天然气股份有限公司 | Multilayer composite metal oxide catalyst and preparation method thereof |
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