CN104649893B - Method for preparing unsaturated acid - Google Patents
Method for preparing unsaturated acid Download PDFInfo
- Publication number
- CN104649893B CN104649893B CN201310585492.0A CN201310585492A CN104649893B CN 104649893 B CN104649893 B CN 104649893B CN 201310585492 A CN201310585492 A CN 201310585492A CN 104649893 B CN104649893 B CN 104649893B
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- CN
- China
- Prior art keywords
- catalyst
- oxidation
- molybdenum
- lanthanum
- oxygen
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000002253 acid Substances 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 169
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000010949 copper Substances 0.000 claims abstract description 48
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 48
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 44
- 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
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 230000003647 oxidation Effects 0.000 claims abstract description 37
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 claims abstract description 27
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 27
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 23
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010937 tungsten Substances 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 150000007513 acids Chemical class 0.000 claims description 8
- 229910052792 caesium Inorganic materials 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 6
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011135 tin Substances 0.000 abstract description 9
- 239000011777 magnesium Substances 0.000 abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 abstract description 5
- 229910052718 tin Inorganic materials 0.000 abstract description 3
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 abstract 2
- 230000007704 transition Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 45
- 235000016768 molybdenum Nutrition 0.000 description 40
- 239000012071 phase Substances 0.000 description 36
- 239000002131 composite material Substances 0.000 description 26
- 239000007789 gas Substances 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 13
- 229910052787 antimony Inorganic materials 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 11
- 150000001875 compounds Chemical class 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 9
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 9
- 229910052758 niobium Inorganic materials 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 229910052684 Cerium Inorganic materials 0.000 description 6
- 229910052785 arsenic Inorganic materials 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 229910052715 tantalum Inorganic materials 0.000 description 6
- 229910018864 CoMoO4 Inorganic materials 0.000 description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 5
- 229910015667 MoO4 Inorganic materials 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 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 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
- 230000009467 reduction Effects 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910017354 Fe2(MoO4)3 Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 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
- 238000009826 distribution Methods 0.000 description 4
- 229910052732 germanium Inorganic materials 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910052701 rubidium Inorganic materials 0.000 description 4
- 229910002900 Bi2MoO6 Inorganic materials 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 229910005809 NiMoO4 Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 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
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- -1 oxo metal compound Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000000859 sublimation Methods 0.000 description 3
- 230000008022 sublimation Effects 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229930194542 Keto Natural products 0.000 description 2
- 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
- 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
- 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
- 238000000498 ball milling Methods 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
- 230000001427 coherent effect Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052734 helium Inorganic materials 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
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 125000000468 ketone group Chemical group 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical compound [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000009418 renovation Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000006104 solid solution Substances 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
- 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
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 1
- BXPKHTBPNOVTOH-UHFFFAOYSA-N C(C=C)(=O)O.CC(=O)C=C Chemical compound C(C=C)(=O)O.CC(=O)C=C BXPKHTBPNOVTOH-UHFFFAOYSA-N 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
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- 229910017010 Fe2 (MoO4)3 Inorganic materials 0.000 description 1
- 229910015142 FeMoO4 Inorganic materials 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910002335 LaNi5 Inorganic materials 0.000 description 1
- 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 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
- 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
- 150000001336 alkenes Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- MGLUJXPJRXTKJM-UHFFFAOYSA-L bismuth subcarbonate Chemical compound O=[Bi]OC(=O)O[Bi]=O MGLUJXPJRXTKJM-UHFFFAOYSA-L 0.000 description 1
- 229940036358 bismuth subcarbonate Drugs 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 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
- 239000003085 diluting agent Substances 0.000 description 1
- XKYFHUXZPRFUTH-UHFFFAOYSA-N dipotassium;dioxido(dioxo)manganese Chemical class [K+].[K+].[O-][Mn]([O-])(=O)=O XKYFHUXZPRFUTH-UHFFFAOYSA-N 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
- 238000001035 drying Methods 0.000 description 1
- 238000001125 extrusion 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
- 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
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-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
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 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
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 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
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect 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
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
- 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
- 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 unsaturated acid, which adopts a fixed bed reactor, wherein reaction raw materials of acrolein or methacrolein, water and oxygen enter the reactor after being preheated by a preheater at a temperature of more than 150 ℃, a salt bath is heated, the temperature of the salt bath ranges from 240 ℃ to 270 ℃, and the space velocity ranges from 800 h to 2400h?1The feed composition is as follows: acrolein or methacrolein 8-15 vol%, water vapor 11-E18 percent, 9-21 percent of oxygen and 60-72 percent of nitrogen by volume; the fixed bed reactor is internally provided with an oxidation catalyst, the catalyst contains molybdenum, vanadium, tungsten, copper, nickel and tin elements, and the catalyst also contains magnesium-based lanthanum hexaaluminate. The catalyst is less likely to undergo phase transition and can produce acrylic acid stably for a long period.
Description
Technical field
The present invention relates to a kind of method that unsaturated aldehyde prepares unsaturated acids, especially acrylic aldehyde or methylacrolein
Selective oxidation prepares the method for acrylic or methacrylic acid.
Background technology
Industrial acrylic aldehyde or the oxidation of aldehydes reaction unit preparing corresponding unsaturated acids of metering system are mainly many
Reaction tube, is ensureing that catalyst is not sintered, on the premise of service life length, improves selectivity and mesh as far as possible
Product yield, conservation, if even if feed stock conversion, acrylic aldehyde, acrylic acid yield improve 0.1～0.5
Percentage point, the amount of the product obtained increases with hundreds of～thousands of tons of level, and its economic benefit is also the most considerable
's.
It is mainly molybdenum system multicomponent catalyst about propylene fraction oxidation acrolein, acrylic acid catalyst.Due to
It is strong exothermal reaction that the acrylic acid reaction of acrylic aldehyde is prepared in Propylene Selectivity oxidation, so being passed through ratio in course of reaction
The steam that heat is big, effectively to remove 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 reduce the activity of catalyst, selectivity, intensity and
Service life, and molybdenum is in the deposition in response system downstream, and blocking pipeline affects the long-term operation of system.
It 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 the highest, but inactivation is fast.Cause many components
It is a lot, wherein because have that Mo-Bi-Co-Fe-O catalyst and Mo-V-O catalysqt deactivation and stability decline
Change including sublimation and the irreversible crystalline phase because of local abnormal high temperature (focus) caused Mo component
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 decaying catalyst being carried out phenetic analysis, 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 related to is the most, such as, for suppressing the loss of molybdenum, CN1583261
Disclose a kind of gas for the gas containing unsaturated aldehyde Yu a kind of molecule-containing keto and carry out selectivity oxygen in the gas phase
Changing the O composite metallic oxide catalyst of reaction, its catalyst consists of: [MoaVbCucXd]Ym[Sbe
Z1 fZ2 g]nOxWherein Mo is molybdenum, and V is vanadium, and Cu is copper, and Sb is antimony, and X is at least selected from tungsten and the one of niobium
Planting element, Y is at least selected from titanium, a kind of element of antimony, Z1It is at least chosen from Fe and a kind of element of nickel,
Z2At least selected from silicon, aluminum, 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 time on the basis of a=12, b is a number of 1 to 6, and c is 0.5 to 4
A number, d is a number of 0.05 to 4, and e is a number of 0.1 to 30, and f is of 0 to 25
Number, 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, 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/or
Copper nitrate makees the catalyst obtained by the raw material of vanadium metal and copper or in addition to above-mentioned raw materials, uses antimony oxidation at a low price
Thing and/or the catalyst that tin-oxide obtains at a low price demonstrate there is a strengthened peak (vanadium-molybdenum at d=4.00
Reactive compound is peculiar) and the V of a strength reduction is had at d=4.382O5Specific peak.So, above-mentioned
The catalyst obtained 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 documentation 2: Japanese Unexamined Patent Publication 8-299797 public affairs
Report, patent documentation 3: Japanese Unexamined Patent Publication 9-194213 publication, patent documentation 4: Japanese Unexamined Patent Application Publication 2004-504288
Number publication；CN102066000A.
For improving the activity of catalyst, selectivity and catalyst life, 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 He the poly-metal deoxide of at least one other metal.
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 be suppression heterogeneously catalysed partial gas phase oxidation acrylic aldehyde be acrylic acid coating catalysqt deactivation, have and change
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
The method producing composite oxide catalysts, the Mo-Bi composite oxide catalytic wherein represented with following chemical formula
The production method of agent includes coherent element source compound to mix form complex in Aquo System and be combined this
Thing carries out heat treatment, uses the one of the waltherite complex of (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 complex: 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 state.Solve Bi
Can in composite oxide catalysts homodisperse problem.Containing α-Bi in catalyst2(MoO4)3、MoO3Fe2
(MoO4)3With β-CoMoO4、y-Bi2MoO6And γ-Bi2MoO6.The open one of CN101690900A
Preparing the preparation method of acrylic aldehyde and acrylic acid catalyst, catalyst is supported thing and inert alumina by active component
Carrier forms；Active component mainly comprises element, selected from Mo, Bi, Co and/or Ni and Fe, also comprises
The trace element 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 that at least one in B, P and W, Z represent 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, bivalence molybdate is mainly beta phase structure, and α phase structure is in active component
Middle content is the lowest 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 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 characterised in that this catalyst is a kind of combined oxidation compositions, contains: (A) containing molybdenum, bismuth and
Ferrum, as the composite oxides of key component, itself is known for urging that described vapor phase catalytic oxidation reacts
Agent, and (B) containing cerium and zirconium as the composite oxides of key component.Catalyst has long catalytic life also
Make to operate steadily in the long term to be possibly realized.Wherein component (B), is the composite oxides represented 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
To absorbing and discharge the promotion functions of oxygen significantly, thus accelerate the oxidation reaction of isobutene., therefore improve
Catalysis activity.Additionally, further suppress component (A) composite oxides caused because of over reduction in time not
Reversible activity reduces (i.e. the stability of composite oxides improves), so that catalytic life extends.This carry
High catalysis activity and the catalytic life extended inhibit reaction temperature to raise in time, thus reduce molybdenum
Distillation at hot spot.This catalyst is used for isobutylene oxidation.
CN102489309A discloses a kind of catalyst preparation for producing acrylic aldehyde and renovation process.Catalyst is
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 anti-carbon deposition ability that catalyst is stronger, catalyst surface not easy-sintering, it is possible to extend the service life of catalyst.
And the renovation process 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 complex, then carries out heat treatment, near
Lack the bismuth subcarbonate 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 compositions 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
Compositions, 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, aluminum and silicon
Composite oxides.CN1321110A is the most respectively using stibium oxide and antimony acetate as activity metal composite oxide
Antimony source.To solve under high-load condition, catalytic mechanical intensity is good, the problem that activity is high.
The open a kind of O composite metallic oxide catalyst of CN200410048021.7, catalyst is by 1. molybdenum, vanadium, copper
Main active component and the most requisite at least by antimony and the stable component of titanium and 3. nickel, ferrum, silicon, aluminum,
The composite oxides of alkali metal, alkaline-earth metal composition.The most 2. and 3. it is 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 a kind of for being existed by acrylic aldehyde or the gas containing acrolein gas and a kind of molecule-containing keto
Carrying out oxidation reaction in vapour phase and produce 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 acrylic aldehyde to produce 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 a kind of acid strength solid acid less than-11.93, 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 tungsten and be partially the face side of this catalyst, and/or
Copper is the core side of this catalyst partially, to improve catalyst activity.Tungsten is the face side of this catalyst partially, and
/ or copper be partially the core side of this catalyst to be difficult to accurately to 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 facies mixed system in 30-100 DEG C；
Keeping organic solvent and water weight ratio is 5～50%；Reaction generates composite oxides presoma serosity；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, there is relatively 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 methylacrolein acrylic acid catalyst of selective oxidation synthesizing methyl of CN1647854, this is urged
The composition formula of agent is: x (Mo12PaKbSbcCudAseAfDgQhOiMoj)/yZ, Z are that carrier dilutes 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, ferrum 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
Add MoO3The heat stability of catalyst, heat conductivility and mechanical strength is improved with carrier heat conduction diluent,
Effectively inhibitory activity component heteropolyacid salt decomposition and reduce 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), its part B comprises and has the X-ray of at least one following copper molybdate and spread out
Penetrate the crystallite (giving the raw data about X-ray diffraction fingerprint in round parentheses) of pattern:
Cu3(MoO4)2(OH)2(lindgrenite, the index card 36-405 of JCPDS-ICDD index (1991)),
Cu4Mo6O20(A.Moini et al., Inorg.Chem.25(21) (1986), 3782-3785), Cu4Mo5O17
(the index card 39-181 of JCPDS-ICDD index (1991)), etc..CN1462211 relates to a kind of system
Standby containing Mo, V, Cu and the method for the multiple-phase multi-metal oxide materials of other optional element.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 in acrylic acid the active material of catalyst used.
[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 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-x Mo3O12, 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 also have the polymetal oxide materials of multicomponent structure
Acrylic acid catalyst is prepared as with the gas phase catalytic oxidation reaction of acrylic aldehyde.In formula, A is
Mo12VaX1bX2 cX3 dX4 eX5 fX6 gOx, B is X1 7CuhHiOy, C is X1 8SbjHkOz, X1For W, Nb,
Ta, Cr and/or Ce.Promoter phase B is made up of the crystallite of these copper molybdate or 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 compositions of one kind of multiple metal-oxides, including the oxidation shape as 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.X1 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
In preparation, containing molybdenum, vanadium, copper and to contain having of one or more elements in elemental tungsten, niobium, tantalum, chromium and cerium 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 containing Cu, Mo and at least one element in element W, V, Nb and Ta
The oxo metal compound of HT copper molybdate structure type.
It addition, under the high temperature conditions, in catalyst, part active component molybdenum loses because of distillation from catalyst surface.
The mixed airflows such as acrylic aldehyde, 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 specified particle diameter and the zirconium of 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 represented
Compound or composite oxides.CN1445020 adds a small amount of tellurium and plays stably free molybdenum trioxide 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 constituted with other element or its hopcalite
The loss of composition catalyst suppression molybdenum.
Accordingly, it is desirable to provide unsaturated aldehyde selective oxidation prepares unsaturated acids catalyst, catalyst activity component
Molybdenums etc. not easily run off, and activity is not susceptible to phase in version mutually, make acrylic aldehyde long period stably selective oxidation
Produce acrylic acid, improve selectivity and the yield of purpose product as far as possible, to obtain bigger economic benefit.
Acrolein selectivity is aoxidized, first has to select the oxidation catalyst of function admirable, secondly also will be in temperature
React under the operating condition of sum, to adapt to industrial high-speed, high selective requirement.Accordingly, it would be desirable to
Develop the acrolein selectivity oxidation technology that a kind of reaction condition relaxes, improve the selectivity of purpose product as far as possible
And yield, long period stably operates, to obtain bigger economic benefit.
Summary of the invention
It is an object of the invention to provide a kind of method that unsaturated aldehyde prepares unsaturated acids, especially acrylic aldehyde or first
The method that the oxidation of base acrolein selectivity produces corresponding unsaturated acids.Particularly suitable acrolein selectivity oxidation system
Standby acrylic acid.React under low temperature, high-load condition, and improve the selectivity of purpose product as far as possible
And yield, long period stably operates, to obtain bigger economic benefit.
A kind of method preparing unsaturated acids, the process conditions of oxidation reaction are limited the most especially, as adopted
Use following process conditions: reaction raw materials acrylic aldehyde or methylacrolein, water, the preheated device of oxygen more than 150 DEG C
Entrance reactor after preheating, salt bath heating, salt temperature 240～270 DEG C, preferably 245～265 DEG C；Air speed
800～2400h-1, preferably 800～1800h-1, feed composition: acrylic aldehyde or methylacrolein 8～15 volume %,
Steam 11～18%, oxygen 9～21 volume %, nitrogen 60～72 volume %；Fixed bed reactors built with
Oxidation catalyst, catalyst contains molybdenum, vanadium, tungsten, copper, nickel and tin element, mainly comprises by following logical formula I
Representing, catalyst is possibly together with magnesio lanthanum hexaaluminate, containing molybdenum, (I) of vanadium and magnesio lanthanum hexaaluminate by 90～98
After kneadings, molding, dry, roasting, finished catalyst is obtained after % and 0.1～the mixing of 10% mass percent.
MoaVbWcCudNieSnfSigMhOx(I).
Wherein: Mo is molybdenum, V is vitriol, and W is tungsten, and Cu is copper, and Ni is nickel, and Sn is stannum, and Si is silicon,
Silicon is the carrier added, and M is at least one element in caesium, lanthanum, manganese；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 2～8, preferably 3～6；
C is a number of 0.5～7, preferably 1.0～4；D is a number of 1～6, preferably 1.0～4；E is 0.5～4
One number, f is a number of 0.1～2, and g is a number of 0.5～50, preferably 1～20, and h is 0.05～2
One number, x is the numerical value determined by the oxygen of each oxide.
The present invention uses propylene two-step oxidizing process to prepare acrylic aldehyde acrylic acid, and one section of Propylene Selectivity aoxidizes propylene processed
Aldehyde, catalyst uses molybdenum-bismuth series catalysts, and two-stage nitration acrolein selectivity oxidation is prepared acrylic acid, used this
Bright catalyst.It is designed with thermocouple inside the present invention one, second stage reactor, is used for measuring reactor each position temperature
Degree, in order to prevent acrylic aldehyde deep oxidation in lower catalyst agent from affecting yield, and makes catalyst coking, this
Bright control acrolein oxidation (two-stage nitration) catalyst lower floor temperature is less than catalyst upper strata temperature, by controlling salt bath
Temperature adjusts reaction bed temperature, and salt temperature is preferably controlled in 245～260 DEG C, is so conducive to catalysis
The long-life of agent uses, and acrolein oxidation reaction can long period steady running.Acrolein oxidation (two of the present invention
Section) catalyst lower floor temperature is less than catalyst upper strata temperature more than at least 3 DEG C.
The present invention is with leading to the preferred lanthanum of M in the catalyst activity component that formula I represents, lanthanum and nickel, copper, stannum
Etc. stable crystal phase structure can be formed, such as Cu2La、LaNi5、La2Ni7, LaSn etc., thus suppressing portion
Point active component molybdenum loses because of distillation from catalyst surface, and active component molybdenum not easily runs off, and delays activity deterioration
Speed, catalyst activity and good stability.With molybdenum, vanadium ratio suitably, in logical formula I, h is 0.05～2 to lanthanum
One number.The preferred Lanthanum (III) nitrate in lanthanum source of the present invention, the preferred sodium stannate of Xi Yuan, stannous chloride.
Catalyst is 92 containing weight/mass percentage composition～the catalyst (I) of 97% and weight/mass percentage composition are
1.5～7% magnesio lanthanum hexaaluminate.
Magnesio lanthanum hexaaluminate oxide of the present invention is prepared according to conventional coprecipitation.As used following method system
Standby: by magnesium nitrate, Lanthanum (III) nitrate and aluminium hydroxide according to LaMgAl11O19Stoichiometric proportion mix homogeneously, add
Enter deionized water and stir, being then spray-dried, gained powder through 160 DEG C be dried after through 1000～1500 DEG C
Roasting 3～12 hours, then by pulverizing or the method such as ball milling obtains particle diameter magnesio six aluminic acid below 20 μm
Lanthanum LaMgAl11O19。
The preparation method of catalyst of the present invention, prepares catalyst (I), magnesio lanthanum hexaaluminate including by coprecipitation,
By catalyst (I), magnesio lanthanum hexaaluminate by 90～98% and 0.1～10% mass percent mixing after through mediate,
Molding, it is dried, obtains 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 mutually phase in version occurs so that catalyst loses activity, and causes active selectable bright
Aobvious decline.Such as activity phase VMo3O11It is changed into MoO3, CoMoO4It is changed into Co3O4, CuMoO4Turn
Become MoO3Deng.
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.The present invention is by magnesio lanthanum hexaaluminate
(LaMgAl11O19) add in catalyst, make active phase more stable, be not susceptible to phase in version thus
Improve catalyst activity and selectivity.
The composite multi-metal oxide catalyst (I) of the present invention uses common preparation method, as adopted
Prepare by following step.
Each unit that M part in compound containing Mo, V, W, Cu, Ni, Sn and logical formula I is related to
Element component composition is dissolved and mix homogeneously in proportion, forms serosity, in slurry production process after being co-precipitated
Adding one or more in silicon dioxide, aluminium oxide or carborundum, dry, molding, roasting obtains catalyst (I).
Catalyst of the present invention (I) and finished catalyst need roasting 3～10h at 350～500 DEG C, compare not
The catalyst of roasting respectively, repeatedly roasting can improve activity and the stability of catalyst.It can be open roasting
Can also be enclosed roasting, calcination atmosphere can be the noble gases such as helium, nitrogen, argon.
The compound of each component of catalyst of the present invention can use the nitrate of each element, ammonium salt, sulphuric acid
Salt, oxide, hydroxide, chloride, acetate etc..As ammonium molybdate, ammonium metavanadate, ammonium paratungstate,
Molybdenum oxide, copper nitrate, copper oxide, Schweinfurt green, nickel nitrate, Lanthanum (III) nitrate, cesium nitrate, potassium manganate, manganese oxide
Deng.
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.
Evaluating catalyst performance index definition is as follows:
Detailed description of the invention
Illustrate that acrylic acid is prepared in acrolein selectivity oxidation with specific embodiment below, but the present invention
Scope is not limited to these embodiments.The analysis method of product composition uses method generally in the art.
Embodiment 1
1. prepare catalyst (I)
Under agitation, take 211.9 grams of ammonium molybdates, ammonium metavanadate 46.8 grams, be dissolved in 500ml pure water
In (water temperature more than 65 DEG C), obtain serosity (1), then take 52.2 grams of ammonium paratungstates, 127.9 grams of copper nitrates,
14.5 grams of nickel nitrates, 48 grams of sodium stannates, 5.8 grams of cesium nitrates be dissolved in 1000ml pure water (water temperature 65 DEG C with
On), it is thoroughly mixed uniformly, obtains serosity (2).Then, serosity (1) mixes with serosity (2),
Obtain serosity (3), i.e. obtain active component serosity (a).10.8 grams are added in active component serosity (a)
Silicon dioxide powder and 1.4 grams of graphite, 80 DEG C of strong stirrings carry out coprecipitation reaction post-heating and are dried, 460 DEG C of roastings
Burn 5 hours, then grind to form the fine powder of below 60 μm, prepared catalyst (I) mainly comprise into:
Mo12V4W2Cu5.5Ni0.5Sn1.8Cs0.3Si1.8Ox
By magnesium nitrate, Lanthanum (III) nitrate and aluminium hydroxide according to LaMgAl11O19Stoichiometric proportion mix homogeneously, add
Enter deionized water and stir, being then spray-dried, gained powder through 160 DEG C be dried after through 1100 DEG C of roastings
10 hours, then obtain particle diameter magnesio lanthanum hexaaluminate LaMgAl below 20 μm by methods such as ball millings11O19。
Take catalyst (I) 94 part, magnesio lanthanum hexaaluminate 6 parts, add deionized water and mediate in kneader,
The extruded hollow columnar granule for φ 4.5 × 5mm, is dried under the conditions of 120 DEG C, and at 450 DEG C, roasting 6.5 is little
Time obtain catalyst 1.
Comparative example 1
Prepare comparative catalyst 1 according to the proportioning that mainly comprises of embodiment 1, but magnesio lanthanum hexaaluminate be not with
The form of solid solution, oxide adds catalyst, but prepares catalyst with coprecipitation method, and reaction condition is with urging
The appreciation condition of agent 1.Comparative catalyst 1 mainly comprise for:
Mo12V4W2Cu5.5Ni0.5Sn1.8Cs0.3Si1.8La0.3Si1.5Mg0.3Al3.3Ox
Oxidation reaction
Fixed bed single tube reactor internal diameter 25mm, inside sets thermocouple, loads along feedstock direction reactor bed
The above-mentioned catalyst of 50ml or comparative example catalyst, salt bath heating, salt temperature 253 DEG C.Pipe enters from the reactions above
Mouth sentences air speed 1350h-1Acrylic aldehyde 9 volume %, oxygen 13 volume %, steam 15 volume %, nitrogen
The mixed gas of 63 volume %.React 24 hours, embodiment 1 and comparative example 1 beds hot(test)-spot temperature
Being respectively 274 DEG C and 269 DEG C, acrolein conversion rate is 99.1% and 98.6%, acrylic acid selectivity 91.2% He
88.3%, acrylic acid yield 89.4% and 86.5%.Through the reaction of 2000 hours, embodiment 1 bed focus
Temperature is respectively 273 DEG C, acrolein conversion rate 99.2%, and acrylic acid (AA) selectivity is 91.0%, propylene
Acid yield 89.3%.In the case of steam intake 15 volume %, through the reaction of 2000 hours, urge
Agent active component molybdenum etc. not easily runs off, and activity is not susceptible to phase in version mutually, during acrolein oxidation,
Reaction bed temperature distribution is more reasonable.Acrylic aldehyde (ACR) and acrylic acid (AA) total recovery 91.0%
Above, catalyst activity component structure is stable, and catalyst has good water repelling property, catalyst performance stabilised.
Comparative example catalyst choice is poor, and acrylic aldehyde, acrylic acid yield are low.
Embodiment 2
The preparation of catalyst 2
Preparation process and primary raw material with embodiment 1 catalyst 1 are identical, simply add 16.2 grams of Lanthanum (III) nitrates,
Catalyst (I) mainly comprises as Mo12V5W4Cu2Ni3.7Sn0.6La0.5Si2.2Ox.Take catalyst (I)
97 parts, magnesio lanthanum hexaaluminate 3 parts, add deionized water and mediate in kneader, through banded extruder extruding, roll
It is a granulated into the ball shape of a diameter of 2mm, within 8 hours, i.e. obtains catalyst 2 through 450 DEG C of roastings.
Fixed bed single tube reactor internal diameter 25mm, inside sets thermocouple, loads along feedstock direction reactor bed
The above-mentioned catalyst of 50ml, salt bath heating, salt temperature 260 DEG C.Tube inlet sentences air speed 1450h from the reactions above-1
Enter acrylic aldehyde 9 volume %, oxygen 13 volume %, steam 17 volume %, nitrogen 61 volume % mixed
Close gas.Reacting 24 hours beds hot(test)-spot temperatures 284 DEG C, acrolein conversion rate is 99.2%, propylene
Acid selectivity 91.3%, acrylic acid yield 89.1%.Through the reaction of 2000 hours, bed hot localised points temperature
Spending 283 DEG C, acrolein conversion rate is 99.1%, acrylic acid selectivity 91.4%, acrylic acid yield 89.0%.
Catalyst activity component molybdenum etc. not easily runs off, and activity is not susceptible to phase in version, purpose selectivity of product and yield mutually
Height, catalyst performance stabilised.
Embodiment 3
Preparation process and primary raw material with embodiment 1 catalyst 1 are identical, simply add 11.8 grams of potassium manganates,
Catalyst (I) mainly comprises as Mo12V2W6.7Cu1Ni1.2Sn1.0Si0.7Mn0.6Ox.Take catalyst (I)
95 parts, magnesio lanthanum hexaaluminate 5 parts, add deionized water and mediate in kneader, extruded through banded extruder be
The hollow columnar granule of φ 4.5 × 5mm, i.e. obtains catalyst 3 in 6 hours through 500 DEG C of roastings.
Fixed bed single tube reactor internal diameter 25mm, inside sets thermocouple, loads along feedstock direction reactor bed
The above-mentioned catalyst of 50ml, salt bath heating, salt temperature 255 DEG C.Tube inlet sentences air speed 2000h from the reactions above-1
Enter acrylic aldehyde 10 volume %, oxygen 14 volume %, steam 15 volume %, nitrogen 61 volume % mixed
Close gas.Reacting 24 hours beds hot(test)-spot temperatures 282 DEG C, acrolein conversion rate is 99.5%, propylene
Acid selectivity 90.3%, acrylic acid yield 89.2%.Through the reaction of 2000 hours, bed hot localised points temperature
Spending 281 DEG C, acrolein conversion rate is 99.3%, acrylic acid selectivity 90.2%, acrylic acid yield 89.6%.
Catalyst activity component molybdenum etc. not easily runs off, and activity is not susceptible to phase in version, purpose selectivity of product and yield mutually
Height, catalyst performance stabilised.
Embodiment 4
Preparation process and primary raw material with embodiment 2 catalyst 2 are identical, catalyst (I) mainly comprise into:
Mo12V8W0.5Cu4Ni2.4Sn0.1Si1.0La1.8Ox.Take catalyst (I) 91 part, magnesio lanthanum hexaaluminate 9 parts,
Add deionized water to mediate in kneader, through the extruded hollow columnar granule for φ 4.5 × 5mm of banded extruder,
Within 6 hours, catalyst 4 is i.e. obtained through 500 DEG C of roastings.
Fixed bed single tube reactor internal diameter 25mm, inside sets thermocouple, loads along feedstock direction reactor bed
The above-mentioned catalyst of 50ml, salt bath heating, salt temperature 245 DEG C.Tube inlet sentences air speed 1200h from the reactions above-1
Enter acrylic aldehyde 8 volume %, oxygen 12 volume %, steam 16 volume %, nitrogen 64 volume % mixed
Close gas.Reacting 24 hours beds hot(test)-spot temperatures 267 DEG C, acrolein conversion rate is 98.9%, propylene
Acid selectivity 90.1%, acrylic acid yield 89.1%.Catalyst activity component molybdenum etc. is difficult to, because of sublimation, live
Property be not susceptible to phase in version mutually, purpose selectivity of product and yield are high, catalyst performance stabilised.
Claims (9)
1. the method preparing unsaturated acids, uses fixed bed reactors, it is characterised in that use following work
Skill condition: reaction raw materials acrylic aldehyde or methylacrolein, water, the preheated device of oxygen preheat laggard for more than 150 DEG C
Enter reactor, salt bath heating, salt temperature 240～270 DEG C, air speed 800～2400h-1, feed composition: third
Olefine aldehydr or methylacrolein 8～15 volume %, steam 11～18%, oxygen 9～21 volume %, nitrogen 60～72
Volume %；Fixed bed reactors are built with oxidation catalyst, and catalyst contains molybdenum, vanadium, tungsten, copper, nickel and stannum
Element, mainly comprises by following formula M oaVbWcCudNieSnfSigMhOx(I) representing, catalyst also contains
There is magnesio lanthanum hexaaluminate, containing molybdenum, (I) of vanadium and magnesio lanthanum hexaaluminate by 90～98% and 0.1～10% mass
Through kneading, molding after percentage mix, it is dried, obtains finished catalyst after roasting；Wherein: silicon is to add
Carrier, M is at least one element in caesium, lanthanum, manganese；O is oxygen；a、b、c、d、e、f、g、
H represents each Elements Atom ratio respectively, and wherein a=12, b are numbers of 2～8, and c is a number of 0.5～7,
D is a number of 1～6, and e is a number of 0.5～4, and f is a number of 0.1～2, and g is the one of 0.5～50
Number, h is a number of 0.05～2, and x is the numerical value determined by the oxygen of each oxide.
Method the most according to claim 1, it is characterised in that described method is applied to acrolein selectivity
Acrylic acid is prepared in oxidation.
Method the most according to claim 2, it is characterised in that salt temperature 245～265 DEG C, air speed
800～1800h-1。
Method the most according to claim 2, it is characterised in that catalyst for oxidation of acrolein bed lower floor temperature
Degree is less than beds upper strata temperature.
Method the most according to claim 1, it is characterised in that containing 92～97% in used catalyst
Catalyst (I) and weight/mass percentage composition are 1.5～7% magnesio lanthanum hexaaluminate.
Method the most according to claim 1, it is characterised in that the preparation method of used catalyst includes using
Catalyst (I), magnesio lanthanum hexaaluminate is prepared, by catalyst (I), magnesio lanthanum hexaaluminate by 90～98 by coprecipitation
After kneadings, molding, dry, roasting, finished catalyst is obtained after % and 0.1～the mixing of 10% mass percent.
Method the most according to claim 1, it is characterised in that in used catalyst (I), b is 3～6
A number, c is a number of 1.0～4, and d is a number of 1.0～4, and g is a number of 1～20.
Method the most according to claim 1, it is characterised in that in used catalyst (I), M is lanthanum, urges
Mainly comprising of agent is represented by (II): MoaVbWcCudNieSnfSigLahOx(II), wherein h is 0.05～2
A number.
The preparation method of catalyst the most according to claim 6, it is characterised in that catalyst (I) and one-tenth
Product catalyst is roasting 3～10h at 350～500 DEG C.
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