CN104649876B - Preparation method of acrolein - Google Patents
Preparation method of acrolein Download PDFInfo
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- CN104649876B CN104649876B CN201310585695.XA CN201310585695A CN104649876B CN 104649876 B CN104649876 B CN 104649876B CN 201310585695 A CN201310585695 A CN 201310585695A CN 104649876 B CN104649876 B CN 104649876B
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- China
- Prior art keywords
- catalyst
- lanthanum
- propylene
- molybdenum
- temperature
- Prior art date
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- 238000002360 preparation method Methods 0.000 title claims description 17
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 title abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 154
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 48
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 48
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 46
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 46
- 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
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 230000003647 oxidation Effects 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 58
- 239000010949 copper Substances 0.000 claims description 52
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- -1 lanthanum-magnesium aluminate Chemical class 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 229910052797 bismuth Inorganic materials 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052792 caesium Inorganic materials 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 238000007493 shaping process Methods 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims 1
- RIAXXCZORHQTQD-UHFFFAOYSA-N lanthanum magnesium Chemical compound [Mg].[La] RIAXXCZORHQTQD-UHFFFAOYSA-N 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 35
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 27
- 239000011777 magnesium Substances 0.000 abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 abstract description 5
- 238000000859 sublimation Methods 0.000 abstract description 3
- 230000008022 sublimation Effects 0.000 abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract 2
- 239000012072 active phase Substances 0.000 abstract 1
- 150000004645 aluminates Chemical class 0.000 abstract 1
- 230000009466 transformation Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 41
- 235000016768 molybdenum Nutrition 0.000 description 40
- 239000002131 composite material Substances 0.000 description 25
- 239000007789 gas Substances 0.000 description 19
- 229910052720 vanadium Inorganic materials 0.000 description 16
- 229910052721 tungsten Inorganic materials 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000010955 niobium Substances 0.000 description 11
- 239000003377 acid catalyst Substances 0.000 description 10
- 229910052787 antimony Inorganic materials 0.000 description 10
- 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
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
- 239000002253 acid Substances 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000047 product 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 6
- 229910015667 MoO4 Inorganic materials 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 6
- 229910052785 arsenic Inorganic materials 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- 229910052715 tantalum Inorganic materials 0.000 description 6
- 229910018864 CoMoO4 Inorganic materials 0.000 description 5
- 229910017354 Fe2(MoO4)3 Inorganic materials 0.000 description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 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
- 238000010438 heat treatment 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
- 239000000843 powder Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 229910002900 Bi2MoO6 Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 229910052732 germanium Inorganic materials 0.000 description 4
- 230000008676 import Effects 0.000 description 4
- 230000002779 inactivation Effects 0.000 description 4
- 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 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 229910052701 rubidium Inorganic materials 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 229910005809 NiMoO4 Inorganic materials 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 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
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 230000001629 suppression Effects 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 206010013786 Dry skin Diseases 0.000 description 2
- 229910015142 FeMoO4 Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-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
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 229910052789 astatine Inorganic materials 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 230000001427 coherent effect Effects 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 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
- 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
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000009418 renovation Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 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
- SAPXNJKQDHJIRE-UHFFFAOYSA-N [Bi+] Chemical compound [Bi+] SAPXNJKQDHJIRE-UHFFFAOYSA-N 0.000 description 1
- BYUANIDVEAKBHT-UHFFFAOYSA-N [Mo].[Bi] Chemical class [Mo].[Bi] BYUANIDVEAKBHT-UHFFFAOYSA-N 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
- 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229940036348 bismuth carbonate Drugs 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000000748 compression moulding Methods 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 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
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass 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
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 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
- 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
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical class [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 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
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 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
- 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
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000011573 trace mineral Substances 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
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing acrolein by propylene oxidation, wherein reaction raw materials of propylene, water and air enter a fixed bed single-tube reactor after being preheated by a preheater at a temperature of more than 120 ℃, the salt bath temperature is 300-340 ℃, and the space velocity is 800-2000 h‑1The feed composition is as follows: 8-15 vol% of propylene and 70-74 vol% of airPercent, 15-21% of water vapor; the fixed bed reactor is filled with oxidation catalyst containing Mo, Bi, Fe, Ni, Co and Cu and comprising Moa′Bib′Fec′Nid′Coe′CufSihAiBjOyThe catalyst also contains magnesium aluminate lanthanum oxide. The catalyst is used for olefin selective oxidation reaction, has active components such as molybdenum and the like which are not easy to lose due to sublimation, and active phases which are not easy to generate phase transformation, and improves the selectivity and the yield of target products. Acrolein and acrylic acid can be stably produced for a long period.
Description
Technical field
The present invention relates to the preparation method of a kind of methacrylaldehyde, more specifically propylene is in the effect of molybdenum bismuth series catalysts
The method that lower selective oxidation prepares methacrylaldehyde.
Background technology
Current industrial main employing propylene two-step oxidizing process prepares methacrylaldehyde acrylic acid, first propylene gas phase catalysis
Oxidation generates methacrylaldehyde, and methacrylaldehyde is reoxidised into acrylic acid.
The reaction unit that methacrylaldehyde is prepared in industrial propylene oxidation is mainly many reaction tubes, is ensureing catalyst not
Be sintered, service life long on the premise of, improve selectively and purpose product yield as far as possible, save raw material,
Even if if feed stock conversion, methacrylaldehyde, acrylic acid yield improve 0.1～0.5 percentage point, the product obtaining
Amount increases with the level of hundreds of～thousands of tons of, and its economic benefit is also very considerable.
It is mainly molybdenum system multicomponent catalyst with regard to propylene fraction oxidation acrolein, acrylic acid catalyst.Due to
It is strong exothermal reaction that the acrylic acid reaction of methacrylaldehyde is prepared in Propylene Selectivity oxidation, so being passed through ratio in course of reaction
The big steam of heat, effectively removing reaction heat, but the active component molybdenum in catalyst etc. are at gas such as steam
Easy loss under the washing away of stream.And, under the high temperature conditions, in catalyst, part active component molybdenum is from catalyst
Surface loses because of distillation.The loss of active component molybdenum cause reducing the activity of catalyst, selectivity, intensity and
Service life, and molybdenum is in the deposition in reaction system downstream, and blocking pipeline affects the long-term operation of system.
In addition, the active component molybdenum etc. in catalyst i.e. enables and keeps not running off, basic before and after the reaction of molybdenum equal size
Change is little, but through long-term operation activity compatible, phase in version easily occurs.Key component bag in catalyst
Include Fe2(MoO4)3、α-Bi2(MoO4)3、CoMoO4And NiMoO4, wherein α-Bi2(MoO4)3It is to live in surface
Property center, plays selective oxidation effect；Fe2(MoO4)3Play redox facilitation；CoMoO4With
NiMoO4Play Stability Analysis of Structures effect.But, catalyst prepared by employing coprecipitation method is many due to component, mistake
Journey is complicated, and catalyst stabilization differs, although initial activity is very high, but inactivation is fast.Cause many components
It is a lot of because have, wherein that Mo-Bi-Co-Fe-O catalyst and Mo-V-O catalyst inactivation and stability decline
Including because sublimation and the irreversible crystalline phase of the caused Mo component of the abnormal high temperature (focus) in local change
Deng.These factors all can cause the change of specificity of catalyst, causes the reduction of catalyst activity and shortens catalysis
The service life of agent.By carrying out phenetic analysis to decaying catalyst, find Fe2(MoO4)3It is reduced into
FeMoO4, and α-Bi2(MoO4)3It is changed into γ-Bi2MoO6。
Solving the problems referred to above, the patent relating to is relatively more, for example, for the loss of suppression molybdenum, CN1583261
Disclose a kind of gas for the gas containing unsaturated aldehyde and a kind of molecule-containing keto and carry out selective oxygen in the gas phase
Changing the O composite metallic oxide catalyst of reaction, its catalyst consists of: [MoaVbCucXd]
lYm[SbeZ1 fZ2 g]nOxWherein Mo is molybdenum, and V is vanadium, and Cu is copper, and Sb is antimony, X be at least selected from tungsten and
A kind of element of niobium, Y is at least to be selected from titanium, a kind of element of antimony, Z1It is a kind of unit of at least chosen from Fe and nickel
Element, Z2Be at least 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 represents the atomic ratio number of its element, and when on the basis of a=12, b is a number of 1 to 6, and c is 0.5
To a number of 4, d is a number of 0.05 to 4, and e is a number of 0.1 to 30, and f is 0 to 25
A number, g is a number of 0.01 to 20；X is by meeting needed for each metallic element combined oxidation state
One number；Catalyst is made up of its each element oxide or composite oxides.
In order to improve the stability of catalyst, the open a kind of acrylic acid catalyst of CN1130172, respectively with partially
Ammonium vanadate and copper nitrate, and with Low Valent Vanadium oxide and/or at a low price Cu oxide part replace ammonium metavanadate and/
Copper nitrate make the raw material of vanadium metal and copper obtained by catalyst or in addition to above-mentioned raw materials, use antimony oxygen at a low price
Compound and/or the catalyst that tin-oxide obtains at a low price demonstrate there is a strengthened peak at d=4.00
(vanadium-molybdenum reactive compound is peculiar) the V having a remitted its fury at d=4.38_2O5Specific peak.So,
Catalyst obtained above has the catalysis 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
Number 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, selectivity and the catalyst life of catalyst, CN200980112659.3 discloses one
Kind comprise the coating catalyst of following components: (a) carrier, before (b) comprises molybdenum oxide or form molybdenum oxide
The ground floor of body compound, (c) comprises the second layer containing molybdenum and the poly-metal deoxide of other metals at least one.
The preferably molybdenum oxide of ground floor is MoO3, the poly-metal deoxide of the second layer is many metals that formula II represents
Oxide: Mo12BiaCrbX1 cFedX2 eX3 fOy.This catalyst is the application type catalyst including carrier.Invention
Purpose is to suppress heterogeneously catalysed partial gas phase oxidation methacrylaldehyde to be acrylic acid coating catalyst inactivation, has and changes
The inactivation performance entered.This invention is not expressly recited catalyst for being catalyzed propylene oxidation acrolein, propylene
The reactivity worth evaluating data of acid, such as conversion ratio, selectivity, yield etc..The open one of CN87103192
Produce the method for composite oxide catalysts, the Mo-Bi composite oxide catalytic wherein representing with following chemical formula
The production method of agent includes coherent element source compound to mix form compound in Aquo System and be combined this
Thing is heat-treated, the one of the waltherite compound of employing (a) Bi and Na or (b) Bi, Na and X or (c) Bi and X
Compound, as Bi source, at least contains required Na and/or X of part wherein in this compound: X represent 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=1-10, 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 states.Solve Bi
Can in composite oxide catalysts homodisperse problem.Catalyst contains α-Bi2(MoO4)3、MoO3Fe2
(MoO4)3With β-CoMoO4、y-Bi2MoO6And γ-Bi2MoO6.The open one of CN101690900A
Preparing the preparation method of methacrylaldehyde and acrylic acid catalyst, catalyst is supported thing and inert alumina by active component
Carrier forms；Active component mainly comprises element, 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；The wherein following table of active component
The formula of stating represents: MoaBibCocNidFeeXfYgZhOiIn formula, X represents at least one of K, Na, Rb and Cs,
Y represents at least one in B, P and W, and Z represents at least one in Mg, Ca, Zn.Live
The ratio that property component is supported on carrier accounts for the 5-70% of overall catalyst weight；Active component is uneven distribution,
CoMoO4、NiMoO4Aluminate Deng divalent metal is positioned at the kernel of catalyst activity component；Fe2(MoO4)3
And the MoO of free state3Invest the outer layer of kernel；And the outermost layer of active component is bismuth molybdate, formation core-
The state of shell layer distributed.In active component, divalence molybdate is mainly beta phase structure, and α phase structure is in active component
Middle content is very low or does not exists.Catalyst has high activity and high stability.CN1280036 mono-kind produces not
Saturated aldehyde and the catalyst of unsaturated carboxylic acid, described production be by make at least one 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 characterised in that this catalyst is a kind of combined oxidation compositions, contains: (A) containing molybdenum, bismuth and
Iron, as the composite oxides of key component, itself is known urging for the reaction of described vapor phase catalytic oxidation
Agent, and (B) contain cerium and the zirconium composite oxides as key component.Catalyst has long catalytic life simultaneously
Make to operate steadily in the long term to be possibly realized.Wherein component (B), is the composite oxides representing by below general formula (2):
CepZrqFrOy.The zirconium oxide of high degree of dispersion inhibits the gathering of cerium oxide, to keep the latter in course of reaction
In to absorbing significantly and the promotion functions of release oxygen, thus accelerate the oxidation reaction of isobutene, therefore improve
Catalysis activity.Additionally, further suppress component (A) composite oxides causing because of over reduction in time
Irreversible activity reduces (i.e. the stability of composite oxides improves), so that catalytic life extends.This
The catalysis activity that improve and the catalytic life extending inhibit reaction temperature to raise in time, thus reduce
Molybdenum is in the distillation of hot spot.This catalyst is used for isobutylene oxidation.
CN102489309A discloses a kind of catalyst preparation for producing methacrylaldehyde and renovation process.Catalyst is
There are the composite oxides of 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 a pore size distribution more concentrated, moderate total pore volume, wherein
The mesopore of about 5-10nm accounts for more than the 70% of total pore size distribution, forms short and thick pore passage structure, and this feature is composed
Give the stronger anti-carbon deposition ability of catalyst, catalyst surface not easy-sintering, the service life of catalyst can be extended.
And the renovation process being provided by the present invention, decaying catalyst carries out 1-3 days calcination processing in an oxidizing atmosphere,
Catalyst activity is suitable with fresh catalyst.CN87103192 produces Mo-Bi-Na composite oxide catalysts and produces
The method of product, the method includes that mixing coherent element source compound forms compound, then is heat-treated, near
Lack the basic bismuth carbonate of the required Na of solid solution part as Bi source compound.The activity of catalyst by means of
Bi and Na imports the catalyst of specific water-insoluble compound formation and is improved greatly.
CN1109803 relates to multimetal oxide compositions, and they have two phase structure and comprise molybdenum, hydrogen, and one
Individual or multiple element phosphor, arsenic, boron, germanium and silicon；And relate to described composition and prepared by catalytic gas phase oxidation
Purposes in terms of methacrylic acid, improves activity and selectivity.The open a kind of poly-metal deoxide of CN1109802
Composition, they have two phase structure and comprise molybdenum, hydrogen, one or more element phosphors, arsenic, boron, germanium and silicon
And copper, improve base acrylic acid activity and selectivity.CN1298861A is then to use to add magnesium, aluminium and silicon
Composite oxides.CN1321110A is then respectively using antimony oxide and antimony acetate as activity metal composite oxide
Antimony source.To solve under high-load condition, catalytic mechanical intensity is good, the high problem of activity.
The open a kind of O composite metallic oxide catalyst of CN200410048021.7, catalyst is by 1. molybdenum, vanadium, copper
Main active component and 2. requisite at least by antimony and titanium stable component and 3. nickel, iron, silicon, aluminium,
Alkali metal, the composite oxides of alkaline-earth metal composition.It 2. and is 3. wherein can be in the range of 120 DEG C to 900 DEG C
Composite oxides prepared by roasting.This catalyst shows the permanent stability under high activity and good selectivity.
CN1121441 discloses and a kind of exists for the gas by methacrylaldehyde or containing acrolein gas and a kind of molecule-containing keto
Carrying out oxidation reaction in vapour phase and producing acrylic acid catalyst, this catalyst includes (A) a kind of composite oxides,
There is molybdenum and vanadium as base stock, and be suitable to by vapor phase catalytic oxidation methacrylaldehyde producing acrylic acid, and (B)
A kind of solid peracid, its acid strength (Ho) is not more than-11.93 (Ho≤-11.93).This invention uses molybdenum vanadium type composite oxygen
Compound combines with the solid acid less than-11.93 for a kind of acid strength, improves the low temperature high activity of catalyst.
The open a kind of acrylic acid catalyst for producing of CN200510059468.9, is characterized in that, at following formula
The oxide of the metallic element composition that MoaVbWcCudOx (1) represents and/or composite oxides are for being catalyzed
In the acrylic acid catalyst for producing of agent composition, 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 be partially that the core side of this catalyst is difficult to accurately control.The open a kind of propylene formoxy-of CN102039143A
Change and prepare the preparation method of acrylic acid catalyst, a) preparation method of composite oxide coating: will containing Mo,
The water-soluble metal salt of V, W, Cu, Sb composition is dispersed in water/organic phase mixed system in 30-100 DEG C；
Organic solvent and water weight ratio is kept to be 5～50%；Reaction generates composite oxides presoma slurries；Pass through again
Distillation, drying, roasting prepare catalyst activity component；B) above-mentioned active component mainly comprises element, is selected from
Mo, V, Cu, W, Sb one of which or several；Wherein active component following formula represents:
MoaVbCucWdSbeOf, this catalyst uses the mixed system of water and lower alcohol to prepare, and catalyst has higher
Specific surface area and special microstructure, have compared with high-ratio surface and difficult drop-off, and bearing capacity can reach
To 50% and more than, solve shorter problem in application type catalyst service life.
The open a kind of acrylic acid catalyst of MAL selective oxidation synthesizing methyl of CN1647854, this is urged
The composition formula of agent is: x (Mo12PaKbSbcCudAseAfDgQhOiMoj)/yZ, Z are carrier dilution heat conduction
Agent；Mo, P, K, Sb, Cu and As are respectively molybdenum, phosphorus, potassium, antimony, copper and arsenic；A represent tungsten W,
At least one element in vanadium V, niobium Nb, iron Fe and lead Pb；D represents boron, gallium Ga, indium In, germanium
At least one element in Ge and silicon Si；Q represents at least one element in rubidium Rb, caesium Cs and thallium Tl, this
Bright one side improves the activity and selectivity of catalyst by adding Sb, Cu and As；On the other hand pass through
MoO3 and carrier heat conduction diluent is added to improve the heat endurance of catalyst, heat conductivility and mechanical strength,
Effectively inhibitory activity component heteropolyacid salt decomposition and reduction beds hot(test)-spot temperature, it is to avoid Mo and
The loss of As, extends catalyst service life.
The open a kind of polymetal oxide materials of CN1109800: in formula, A is Mo12VaXb 1Xc 2
Xd 3Xe 4Xf 5Xg 6Ox(coexisting phase), the X-ray that its part B comprises to have at least one following copper molybdate is spread out
Penetrate the crystallite (giving the firsthand information about X-ray diffraction fingerprint in round parentheses) of pattern:
Cu3(MoO4)2(OH)2(lindgrenite, the card index 36-405 of JCPDS-ICDD index (1991)),
Cu4Mo6O20(A.Moini et al., Inorg.Chem.25(21) (1986), 3782-3785), Cu4Mo5O17
(the card index 39-181 of JCPDS-ICDD index (1991)), etc..CN1462211 relates to a kind of system
The standby method containing Mo, V, Cu and the multiple-phase multi-metal oxide materials of other optional elements.According to this
Invention, at least one phase is pre-formed independently, and in the precursor material of the plastically deformable being dispersed in another phase.
Then this mixture is dried and calcines.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), phase A in multimetal oxide compositions, B and C can be unbodied and/or
Crystallization.Phase B is advantageously made up of the crystallite of oxometallate, or comprises that there is X-ray diffraction
Pattern and and then the crystalline substance of oxometallate crystallite copper molybdate of crystal structure types of at least one following copper molybdate
Body structure class α-CuMo4[the registration card 22-242 of JCPDS-ICDD card index, (1991)],
Cu6Mo5O18[the registration card 40-865 of JCPCS-ICDD card index, (1991)], Cu4-xMo3O12, its
Middle x=0-0.25 [registration card 24-56 and 26-547 of JCPCS-ICDD card index, (1991)], etc..Should
Catalyst is to improve selectivity.
Polymetal oxide materials [A] p [B] q [C] r (I) of the open a kind of formula of CN1295499 (I), with containing molybdenum,
Vanadium, copper and antimony and one or more other metals specific the polymetal oxide materials with multicomponent structure
Prepare acrylic acid catalyst as with the gas phase catalytic oxidation reaction of methacrylaldehyde.In formula, A is
Mo12VaX1bX2 cX3 dX4 eX5 fX6 gOx, B is X1 7CuhHiOy, C is X1 8SbjHkOz, X1For W, Nb,
Ta, Cr and/or Ce.Co-catalyst phase B is made up of the crystallite of these copper molybdate or micro-containing such copper molybdate
Brilliant: α-CuMoO4[the reference diffraction pattern in the index card 22-242 of JCPDS-ICDD retrieval 1991],
Cu6Mo5O18[the reference diffraction pattern in the index card 40-865 of JCPDS-ICDD retrieval 1991], Cu4-x
Mo3O12Wherein, x is the 0-0.25 [reference in index card 24-56 and 26-547 of JCPDS-ICDD retrieval 1991
Diffraction pattern], etc..Region C can have metaantimmonic acid copper Cu9Sb4O19The crystallite of structure or Cu4SbO4.5Structure micro-
Brilliant.CN1093950 discloses the composition of one kind of multiple metal oxides, including as the oxidation shape of basis
Mo, V, W, Cu, Ni of formula, its premise is to there is following ratio: Mo:V=12:1 between each elemental composition
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 relate to containing Cu, Mo and at least one selected from element W,
The oxo metal compound of the HT copper molybdate structure type of the element in V, Nb and Ta, its preparation method, and they
Preparation containing molybdenum, vanadium, copper and contain elemental tungsten, niobium, tantalum, in chromium and cerium one or more elements have many
Application in the composite metal oxide material of phase structure.CN1394812 is at the catalysis gas for organic compound
Phase oxidation reaction catalyst in use poly-metal deoxide, described poly-metal deoxide contain Mo, V and
At least one in element W, Nb, Ti, Zr, Hf, Ta, Cr, Si and Ge, and it is former to have special three-dimensional
Son arrangement.CN1500770 contains molybdenum, vanadium, copper and contains in elemental tungsten, niobium, tantalum, chromium and cerium a kind of or many
Planting the composite metal oxide material having heterogeneous structure of element, they are by catalytic gas phase oxidation of acrolein system third
Application in olefin(e) acid, and contain Cu, Mo and at least one element in element W, V, Nb and Ta
The oxo metal compound of HT copper molybdate structure type.
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 activity that also can make in catalyst
Component runs off.For suppression molybdenum distillation loss cause activity decay, CN1121504 by mix copper component and
There is the zirconium of specified particle diameter and specific surface area and/or titanium and/or cerium, dissipation effect and the mistake of molybdenum composition can be suppressed
Degree reduction.Catalyst includes by lower formula (I) MOaVbWcCudXeYf(I) oxygen of the metallic element composition representing
Compound or composite oxides.CN1445020 adds a small amount of tellurium to play the molybdenum trioxide stably dissociating and copper molybdate
The effect of crystal structure, sublimation and the over reduction of molybdenum have suppressed；CN1583261 with molybdenum, vanadium,
Copper, tungsten and/or niobium are key component, the composite oxides constituting with other elements or its hopcalite
The loss of composition catalyst suppression molybdenum.
Accordingly, it is desirable to provide methacrylaldehyde, acrylic acid catalyst are prepared in Propylene Selectivity oxidation, at acrolein oxidation
Reaction can be carried out under low temperature, high-load condition.Temperature of reactor distribution is more reasonable, and active component molybdenum etc. is no
Being easy to run off, and activity being not susceptible to phase in version mutually, purpose selectivity of product and yield are high.
For Propylene Selectivity oxidation, first have to select the oxidation catalyst of function admirable, secondly also will be in gentleness
Operating condition under react, to adapt to industrial high-speed, high selective to require.Accordingly, it would be desirable to open
The Propylene Selectivity oxidation technology sent out reaction condition a kind of and relax.Improve selectivity and the receipts of purpose product as far as possible
Rate, to obtain bigger economic benefit.
Content of the invention
In order to solve above-mentioned technical problem, it is an object of the invention to provide a kind of Propylene Selectivity oxidation and produce propylene
Aldehyde, acrylic acid.
The method that methacrylaldehyde is prepared in the Propylene Selectivity oxidation that the present invention provides is as follows: use the reaction of fixed bed single tube
Device；Entrance reactor after more than the 120 DEG C preheatings of the preheated device of reaction raw materials propylene, water, air, salt bath heating,
Reaction process condition is: salt temperature 300～340 DEG C, preferably 305～325 DEG C；Air speed 800～2000h-1, excellent
Select 800～1500h-1, feed composition: propylene 8～15 volume %, air 70～74 volume %, steam 15～21%；
Fixed bed reactors are built with oxidation catalyst, and catalyst contains molybdenum, bismuth, iron, nickel, cobalt and copper, main
Form by formula M oa′Bib′Fec′Nid′Coe′CufSihAiBjOy(I) represent, wherein: Mo is molybdenum, Bi
Being bismuth, Fe is iron, and Ni is nickel, and Co is cobalt, and Cu is copper, and Si is silicon, and silicon is the load adding in catalyst
Body, A is at least one element in caesium, calcium or barium；B be in titanium, zinc, potassium, lanthanum at least
A kind of element；O is oxygen；A ', b ', c ', d ', e ', f, h, i, j represent each Elements Atom ratio respectively, wherein
A ' is a number of 12-14, and b ' is a number of 1-6, preferably 1.2-5；C ' is a number of 0.2-5, preferably
0.5-3.5；D ' is a number of 1-6, preferably 1.5-4；E ' is a number of 0.5-6, and preferably 1.5-4.5, f are
One number of 0.2-4, h is a number of 0.1-30, and i, j are numbers of 0.05-2.5, and y is by each oxidation
The numerical value that the oxygen of thing determines.Catalyst is possibly together with lanthanum-magnesium aluminate oxide (LaMgAl11O19), containing molybdenum, bismuth
(I) and lanthanum-magnesium aluminate oxide by 90～98% and 0.5～10% mass percent mixing after through mediate, shaping,
Obtain finished catalyst after drying, roasting.
Inside reactor of the present invention is provided with thermocouple, is used for measuring each spot temperature of reactor, in order to prevent propylene
In lower catalyst agent, deep oxidation affects reaction yield, and makes catalyst coking, and the present invention controls under catalyst
Layer temperature is less than catalyst upper strata temperature, adjusts reaction bed temperature, salt bath temperature by controlling salt temperature
Degree is preferably controlled in 305～325 DEG C, is so conducive to the long-life of catalyst to use, and propylene oxidation reaction can
Long period steady running.Beds lower floor temperature is less than beds upper strata temperature more than 3 DEG C.
Lanthanum-magnesium aluminate oxide of the present invention is prepared according to conventional coprecipitation.As used following method to prepare: will
Magnesium nitrate, lanthanum nitrate and aluminium hydroxide are according to LaMgAl11O19Stoichiometric proportion mix, add depart from
Sub-water simultaneously stirs, and is then spray-dried, gained powder after 160 DEG C of dryings through 1000～1500 DEG C of roastings
3～12 hours, then obtain lanthanum-magnesium aluminate below 20 μm for the particle diameter by methods such as pulverizing or ball millings
LaMgAl11O19。
It is highly preferred that catalyst contains (I) 92～97%, also lanthanum-magnesium aluminate oxide 2～8%.
The catalyst activity component that the present invention (I) represents is preferably added to active component lanthanum, lanthanum and bismuth, cobalt,
Copper can form stable crystal phase structure, such as BiLa, BiLa2、Co3La2、Cu2La etc., the good dispersion of molybdenum,
Thus suppress part active component molybdenum to lose from catalyst surface because of distillation, active component molybdenum etc. not easily runs off,
Before and after catalyst reaction, active component molybdenum content is basically unchanged, and delays activity deterioration rate, catalyst activity and steady
Qualitative good.Lanthanum is suitable with molybdenum, cobalt ratio, and in formula (I), B is lanthanum, and i is a number of 0.1～1.5, j
Being a number of 0.1～3, the addition of too much lanthanum can compete molybdenum with bismuth, cobalt and iron, affects catalyst activity.Urge
Agent mainly comprises and is represented by formula (II): Moa′Bib′Fec′Nid′Coe′CufSihAiLajOy(II).
The multi-metal-oxide catalyst (I) of the present invention uses common preparation method, as used
Prepared by following step, will be containing Mo, A in Bi, Fe, the compound of Co, Ni, Cu and formula (I)iBj
The each elemental constituent compound relating to dissolve and mix, after being co-precipitated formed slurries, prepared by slurries
During add silica, one or more in aluminum oxide or carborundum, dry, shaping, roasting must be urged
Agent (I).
The preparation method of catalyst of the present invention, including prepare catalyst (I), lanthanum-magnesium aluminate oxidation by coprecipitation
Thing, by catalyst (I), lanthanum-magnesium aluminate oxide by warp after 90～98% and 0.5～10% mass percent mixing
Mediate, shaping, be dried, obtain finished catalyst after roasting.
Under Oxygen Condition, catalyst molybdenum isoreactivity component under the high temperature conditions is not only easy to run off, and activity phase
Being susceptible to phase in version, activity occurs phase in version to cause active selectable to be decreased obviously mutually.Such as activity phase
CoMoO4It is converted into Co3O4, CuMoO4It is changed into MoO3, Fe2(MoO4)3It is transformed into FeMoO4,
α-Bi2(MoO4)3It is changed into γ-Bi2MoO6Deng.
Active component molybdenums in catalyst etc. i.e. enable holding and do not run off, and before and after the reaction of molybdenum equal size, basic change is not
Greatly, but easily there is phase in version through long-term operation activity compatible.Lanthanum-magnesium aluminate oxide is added by the present invention
In catalyst, make active phase more stable, be not susceptible to phase in version thus improve catalyst activity and selection
Property.
Catalyst of the present invention (I) and finished catalyst are required for roasting 3～10h at 400～580 DEG C, compare
Not distinguishing the catalyst of roasting, repeatedly roasting can improve activity and the stability of catalyst.It can be open roasting
Burning also can be enclosed roasting, and 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 of each element, ammonium salt, sulfuric acid
Salt, oxide, hydroxide, chloride, acetate etc., such as lanthanum nitrate, magnesium nitrate, calcium chloride, chlorination
Calcium, brium carbonate, barium nitrate, potassium nitrate, zinc nitrate, titanium dioxide, calcium hydroxide, strontium nitrate, ferric nitrate,
Iron oxide, cobalt nitrate, cobalt oxide, bismuth nitrate, ammonium molybdate etc..
After catalyst slurry of the present invention is dried, it is usually preferred to use extrusion molding, granulating and forming, compression molding etc.
Forming method is processed into spherical, hollow spheres, ellipticity, cylindric, hollow circuit cylinder etc., preferably hollow circle
Post or spherical.
The present invention, in order to improve intensity, the efflorescence degree of catalyst, can add glass in above-mentioned catalyst (I)
In fiber, graphite, ceramic or various whisker one or more.
Evaluating catalyst performance index definition is as follows:
Detailed description of the invention
With specific embodiment the method that methacrylaldehyde is prepared in Propylene Selectivity oxidation is described below, but the model of the present invention
Enclose and be not limited to these embodiments.The propylene that following example use is propylene content >=99.6%(volume fraction)
High concentration propylene.The analysis method of product composition uses method generally in the art.
Embodiment 1
Under agitation, take 236.5 grams of ammonium molybdates and be dissolved in 1000ml pure water (water temperature more than 65 DEG C),
Obtain slurries (1), then take 89.1 grams of cobalt nitrates, 64 grams of nickel nitrates, 115.9 grams of ferric nitrates, 22.3 grams of nitre
Acid copper, 34.2 grams of lanthanum nitrates are dissolved in 500ml pure water (water temperature more than 65 DEG C), are thoroughly mixed uniformly,
Obtain slurries (2).Take 162.5 grams of bismuth nitrates again, be dissolved under agitation in dust technology, obtain slurries (3).
Then, slurries (1) mix with slurries (2), obtain slurries (4), then slurries (3) are added slurries
(4), in, add 3.8 grams of titanium dioxide and 4 grams of graphite, obtain active component slurries (a).By activity
Component slurries (a) and 7.4 grams of silicon dioxide powders carry out coprecipitation reaction, and heated drying, with 150 DEG C in nitrogen
Be heat-treated 3 hours, then 500 DEG C of roastings 4 hours, size-reduced, grind, process of sieving obtain 40 μm with
Under fine powder, be i.e. catalyst (I) powder, mainly comprise for:
Mo13Bi3.3Fe2.8Ni2.1Co3.0Cu0.93Si1.2La1.0Ti0.46Oy(I)
By magnesium nitrate, lanthanum nitrate and aluminium hydroxide according to LaMgAl11O19Stoichiometric proportion mix, add
Enter deionized water and stir, being then spray-dried, gained powder after 160 DEG C of dryings through 1100 DEG C of roastings
10 hours, then obtain lanthanum-magnesium aluminate LaMgAl below 20 μm for the particle diameter by methods such as ball millings11O19。
Take catalyst (I) 93 part, lanthanum-magnesium aluminate oxide 7 parts, add deionized water and mediate in kneader,
The extruded hollow columnar particle for φ 4.5 × 5mm, is dried under the conditions of 120 DEG C, and at 450 DEG C, roasting 6.5 is little
When obtain catalyst 1.
Comparative example 1
Prepare comparative catalyst 1 according to the proportioning that mainly comprises of embodiment 1, but lanthanum-magnesium aluminate is not with solid solution
The form of oxide body adds catalyst, but prepares catalyst with coprecipitation method, the same catalyst of reaction condition
The appreciation condition of 1.Comparative catalyst 1 mainly comprise for:
Mo13Bi3.3Fe2.8Ni2.1Co3.0Cu0.93Si1.2La1.3Ti0.46Mg0.3Al3.3Oy
Propylene method for oxidation
Fixed bed single tube reactor internal diameter 25mm, inside sets thermocouple, along propylene feed orienting response device bed dress
Enter the above-mentioned catalyst of 50ml or comparative example catalyst, salt bath heating, salt temperature 310 DEG C.From the reactions above
Tube inlet sentences air speed 1200h-1Import propylene 9 volume %, air 72 volume %, steam 19 volume %
Mixed gas.Reacting 24 hours, bed hot localised points temperature 363 DEG C, beds upper temp is high
In beds bottom bed temperature 3 DEG C.Propylene conversion 99.0%, acrolein selectivity 88.6%, third
Olefine aldehydr yield 81.1%, acrolein+acrylic acid yield 91.7%.Temperature Distribution is more reasonable, is conducive to catalysis
Agent long period steady running.Through the reaction of 2000 hours, bed hot localised points temperature 362 DEG C, catalyst
Bed upper temp is higher than beds bottom bed temperature 3 DEG C.Propylene conversion 98.8%, methacrylaldehyde selects
Selecting property 88.4%, methacrylaldehyde yield 80.9%, acrolein+acrylic acid yield 91.2%.Active component molybdenum etc. is difficult to
Running off, activity is not susceptible to phase in version mutually, and catalyst structure is stable, improves selectivity and the receipts of purpose product
Rate, meets device long period steady running.Comparative example catalyst 1 oxidation reaction sample analysis in 24 hours,
Bed hot localised points temperature 364 DEG C, propylene conversion 97.9%, acrolein selectivity 84.9%, methacrylaldehyde is received
Rate 74.6%, acrolein+acrylic acid yield 86.3%.Comparative example catalyst choice difference, methacrylaldehyde, propylene
Acid yield is low.
Embodiment 2
Preparation process and major part raw material with embodiment 1 catalyst 1 are identical, through 500 DEG C of roastings within 4 hours, are
Catalyst (I), mainly comprise as Mo13Bi4.2Fe4Ni3Co3.6Cu0.3Si2.2Ba0.3K0.4Oy(I).Take
Catalyst (I) 90 part, lanthanum-magnesium aluminate oxide 10 parts, add deionized water and mediate in kneader, extruding
Being shaped to the hollow columnar particle of φ 4.5 × 5mm, being dried under the conditions of 120 DEG C, roasting at 550 DEG C obtains for 4 hours
Catalyst 2.
Fixed bed single tube reactor internal diameter 25mm, inside sets thermocouple, along propylene feed orienting response device bed dress
Enter the above-mentioned catalyst of 50ml 2, salt bath heating temperature 315 DEG C.Tube inlet sentences air speed 1000h from the reactions above-1
Import propylene 9 volume %, air 71 volume %, the mixed gas of steam 21 volume %, oxidation reaction
Sample analysis after 24 hours, bed hot localised points temperature 365 DEG C, propylene conversion 99.2%, methacrylaldehyde selects
Property 88.5%, methacrylaldehyde yield 81.5%, acrolein+acrylic acid yield 91.6%.Oxidation reaction 2000 hours
Rear sample analysis, bed hot localised points temperature 363 DEG C, propylene conversion 99.1%, acrolein selectivity 88.7%,
Methacrylaldehyde yield 81.6%, acrolein+acrylic acid yield 91.5%.
Embodiment 3
Preparation process and primary raw material with embodiment 1 catalyst 1 are identical, through 450 DEG C of roastings 5 hours and get final product
Catalyst (I).Mainly comprise as Mo14Bi5Fe2.5Ni4Co4Cu2Si3.5K0.2La1.8Oy(I).Take and urge
Agent (I) 95 part, lanthanum-magnesium aluminate oxide 5 parts, add deionized water and mediate in kneader, be squeezed into
Type is the hollow columnar particle of φ 4.5 × 5mm, is dried under the conditions of 120 DEG C, and roasting at 550 DEG C is urged for 4 hours
Agent 3.
Fixed bed single tube reactor internal diameter 25mm, inside sets thermocouple, along propylene feed orienting response device bed dress
Enter the above-mentioned catalyst of 50ml, salt bath heating temperature 305 DEG C.Tube inlet sentences air speed 900h from the reactions above-1
Import propylene 8 volume %, air 71 volume %, the mixed gas of steam 21 volume %.Oxidation reaction
After 24 hours, bed hot localised points temperature 345 DEG C, propylene conversion 98.9%, acrolein selectivity 88.2%,
Methacrylaldehyde yield 81.1%, acrolein+acrylic acid yield 91.2%.
Embodiment 4
Preparation process and primary raw material with embodiment 1 catalyst 1 are identical, through 400 DEG C of roastings 7 hours and get final product
Catalyst (I).Mainly comprise as Mo14Bi6Fe5Ni6Co5.8Cu3.8Si1.8Cs0.2La3.3Oy(I).Take and urge
Agent (I) 97 part, lanthanum-magnesium aluminate oxide 3 parts, add deionized water and mediate in kneader, be squeezed into
Type is the hollow columnar particle of φ 4.5 × 5mm, is dried under the conditions of 120 DEG C, and roasting at 500 DEG C is urged for 5 hours
Agent 4.
Fixed bed single tube reactor internal diameter 25mm, inside sets thermocouple, along propylene feed orienting response device bed dress
Enter the above-mentioned catalyst of 50ml 3, salt bath heating temperature 325 DEG C.Tube inlet sentences air speed 1800h from the reactions above-1
Import propylene 10 volume %, air 71 volume %, the mixed gas of steam 19 volume %.Oxidation reaction
After 24 hours, bed hot localised points temperature 370 DEG C, propylene conversion 99.4%, acrolein selectivity 88.8%,
Methacrylaldehyde yield 82.1%, acrolein+acrylic acid yield 92.7%.After oxidation reaction 2000 hours, bed office
Portion's hot(test)-spot temperature 368 DEG C, propylene conversion 99.2%, acrolein selectivity 88.9%, methacrylaldehyde yield 81.8%,
Acrolein+acrylic acid yield 92.5%.
Claims (11)
1. the preparation method of a methacrylaldehyde, it is characterised in that；The preheated device of reaction raw materials propylene, water, air 120 DEG C with
Entering reactor after upper preheating, reaction process condition is: salt temperature 300～340 DEG C, air speed 800～2000h-1,
Feed composition: propylene 8～15 volume %, air 70～74 volume %, steam 15～21%；Fixed bed
Reactor is built with oxidation catalyst, and catalyst contains molybdenum, bismuth, iron, nickel, cobalt and copper, mainly comprises by formula
Moa ' Bib ' Fec ' Nid ' Coe ' CufSihAiBjOy (I) represents, wherein silicon is carrier, and A is to be selected from
At least one element in caesium, calcium or barium；At least one element in titanium, zinc, potassium, lanthanum for the B；O is oxygen；a′、
B ', c ', d ', e ', f, g, h, i, j represent each Elements Atom ratio respectively, and wherein a ' is a number of 12-14,
B ' is a number of 1-6, and c ' is a number of 0.2-5, and d ' is a number of 1-6, and e ' is a number of 0.5-6,
F is a number of 0.2-4, and h is a number of 0.1-30, and i, j are numbers of 0.05-2.5, and y is by each oxide
Oxygen determine numerical value；Catalyst, possibly together with lanthanum-magnesium aluminate, presses 90～97% containing molybdenum, (I) of bismuth and lanthanum-magnesium aluminate
Obtain finished catalyst with after 3～10% mass percents mixing after kneading, shaping, drying, roasting.
2. method according to claim 1, it is characterised in that salt temperature 305～325 DEG C.
3. method according to claim 1, it is characterised in that air speed 800～1500h.
4. method according to claim 1, it is characterised in that beds lower floor temperature is less than beds upper strata temperature.
5. method according to claim 4, it is characterised in that beds lower floor temperature is less than beds upper strata temperature
More than 3 DEG C.
6. method according to claim 1, it is characterised in that used catalyst contains (I) 92～97%, also aluminic acid
Magnesium lanthanum 3～8%.
7. method according to claim 1, it is characterised in that in used catalyst (I), b ' is a number of 1.2-5, c '
Being a number of 0.5-3.5, d ' is a number of 1.5-4, and e ' is a number of 1.5-4.5.
8. method according to claim 1, it is characterised in that in used catalyst (I), B is lanthanum, and i is 0.1～1.5
A number, j is a number of 0.1～2.5, mainly comprise by formula (II) represent: Moa ' Bib ' Fec '
Nid′Coe′CufSihAiLajOy(Ⅱ)。
9. the method according to any one of claim 6～8, it is characterised in that the preparation of used catalyst (I) includes
Following steps: will be containing Mo, AiBj's relates in Bi, Fe, the compound of Co, Ni, Cu and formula (I)
Each elemental constituent compound dissolves and mixes, and forms slurries after being co-precipitated, and adds titanium dioxide in slurry production process
One or more in silicon, aluminum oxide or carborundum etc., dry, and shaping, roasting obtains catalyst (I).
10. method according to claim 1, it is characterised in that the preparation method of used catalyst includes being prepared by coprecipitation urging
Catalyst (I), lanthanum-magnesium aluminate are pressed 90～96% and 5～10% mass percents by agent (I), lanthanum-magnesium aluminate
Obtain finished catalyst after kneading, shaping, drying, roasting after mixing.
11. methods according to claim 10, it is characterised in that catalyst (I) and finished catalyst be required for 400～
Roasting 3～10h at 580 DEG C.
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