CN102989480B - Composite multi-metal oxide catalyst and preparation method thereof - Google Patents
Composite multi-metal oxide catalyst and preparation method thereof Download PDFInfo
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- CN102989480B CN102989480B CN201110265250.4A CN201110265250A CN102989480B CN 102989480 B CN102989480 B CN 102989480B CN 201110265250 A CN201110265250 A CN 201110265250A CN 102989480 B CN102989480 B CN 102989480B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 295
- 238000002360 preparation method Methods 0.000 title claims abstract description 65
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 36
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011733 molybdenum Substances 0.000 claims abstract description 32
- 239000010949 copper Substances 0.000 claims abstract description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 13
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 10
- 239000011777 magnesium Substances 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010937 tungsten Substances 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 239000011572 manganese Substances 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 61
- 239000002002 slurry Substances 0.000 claims description 60
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 48
- 239000000377 silicon dioxide Substances 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000470 constituent Substances 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 20
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 19
- 229910052622 kaolinite Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 17
- 229910052746 lanthanum Inorganic materials 0.000 claims description 15
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- 238000000975 co-precipitation Methods 0.000 claims description 10
- 239000010955 niobium Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical group [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical group [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 50
- 230000000694 effects Effects 0.000 abstract description 21
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000009825 accumulation Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 106
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 38
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 21
- 238000007254 oxidation reaction Methods 0.000 description 20
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 18
- 230000003647 oxidation Effects 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 238000001125 extrusion Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 239000012018 catalyst precursor Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- 229910052787 antimony Inorganic materials 0.000 description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 235000018660 ammonium molybdate Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical class [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical class [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical class [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910052714 tellurium Inorganic materials 0.000 description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- -1 overall structure Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-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-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical class [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
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- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical class [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical class [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
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- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000000576 supplementary effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a composite multi-metal oxide catalyst and a preparation method thereof, which is characterized in that the composition of the catalyst can be represented by Mo in the following general formula aVbWcNidAeBfSigOx(I) Wherein: mo is molybdenum, V is vanadium, W is tungsten, Ni is nickel, Si is silicon, Si is a carrier added in the catalyst, A is at least one element selected from copper, cobalt and manganese; b is at least one element selected from the group consisting of zirconium, strontium, magnesium and titanium. The catalyst can effectively reduce local heat accumulation of the fixed bed single-pipe reactor, inhibit the formation of hot spots, and has the characteristics of high reaction activity and selectivity and long service life.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method of compound poly-metal deoxide, for catalyzing propone formoxy-ization acrylic acid processed.
Background technology
Industrial main employing propylene two-step oxidizing process is prepared acrylic acid at present, and first propylene catalytic gas phase oxidation generates methacrylaldehyde, and methacrylaldehyde is reoxidised into acrylic acid.Acrolein oxidation reaction is strong exothermal reaction, in beds, can produce focus, the heat that moment is gathered is constantly accumulated, by cause catalyst activity component loss, come off, to such an extent as to catalyst activity reduction, the lost of life, and cause, because over oxidation reacts the formation that aggravates accessory substance, even causing runaway reaction, make sintering of catalyst.
The appearance of " progress of oxidation acrylic acid synthesizing process and catalyst " (petrochemical industry, the 39th the 7th phase of volume in 2010) social focus also can make catalyst damage evil, shortens the service life of catalyst.Taking 80,000 tons/year of acroleic acid devices as example, propylene oxidation is prepared and in acrolein reaction device, is needed more than 2.5 ten thousand tubulation, acrolein oxidation to prepare in acrylic acid reactor also to need more than 2.5 ten thousand tubulation, load altogether more than 100 ton of methacrylaldehyde, acrylic acid catalyst.More than 50000 reaction tube, the filling of catalyst ensures not fill empty certain difficulty that has, if because focus is crossed the very fast sintering of high catalyst, again change in a short time agent, it is huge can envisioning its economic loss again; In addition, for methacrylaldehyde, acrylic acid production, carry out as much as possible under cryogenic conditions, because reaction needed salt bath heating, its energy resource consumption that maintains production is also huge spending; Due to the generation of focus, high temperature resistant to the requirement of reaction tube tubing, for up to ten thousand reaction tubes, tubing expense is exactly a very large cost.Therefore,, if effectively suppress the generation of beds focus, can bring huge economic benefit to large-scale industrial production.
At present, there is several different methods can reduce or avoid gathering and peroxidization of focus, can be from the viewpoint of the improvement of the improvement of reaction unit and catalyst two.Aspect catalyst, as: Japanese patent laid-open 04-217932 has proposed the method for the hot polymerization collection on a kind of appearance or focus that suppresses focus, by preparing the multiple catalyst with different possessive volumes, and the mode reducing to outlet one side catalyst possessive volume from unstripped gas inlet side, fill successively reaction tube, but the possessive volume of catalyst is subject to the restriction of reaction tube diameter, and it is also very difficult that multiple catalysts is filled into reaction tube.Japanese Unexamined Patent Publication 10614/1972, US200421442A sneak into heat resistanceheat resistant point to form catalyst are inert substance with by catalyst dilution in catalyst, and Japanese Patent Publication 36739/1987 is made catalyst the method for tubulose.There is again the Catalyst packing that unstrpped gas porch reduces by active component.CN200510007929.8 provides a kind of catalyzing propone aldehyde gaseous oxidation system acrylic acid catalyst, described catalyst comprises molybdenum and vanadium, also comprise at least one volatile catalyst toxic component, its amount is 10 to 100ppb quality through ion chromatography measurement, this catalyst can reduce the temperature of hot spot, and suppresses the reduction of the reaction efficiency of thermal degradation.Specific practice is that, by the volatility toxic component of specified quantitative being comprised and originally having in highly active catalyst, catalytic activity declines momently, can reduce the temperature of hot spot.CN97104224.1 is by after dividing catalytic active component and being loaded on carrier, calcines the generation that the catalyst of load sharing suppresses focus, and the average grain diameter of catalyst is 4～16mm, and the average grain diameter of carrier is 3～12mm, and calcining heat is 500～600 DEG C.CN01111960.8 provides the catalyst of a kind of Mo-W-Bi-Fe of containing, this catalyst is by the mode that changes the kind of possessive volume calcining heat and/or alkali metal and/or quantity and increase to outlet one side from the inlet side of unstripped gas according to catalyst activity, fills successively reaction zone with described multiple types catalyst.Catalyst is at least divided into two-layer in the axial direction of reaction tube, and this catalyst is the multiple types catalyst with different activities level, can be by changing calcining heat and/or wherein kind and/or the quantity of alkali metal obtain.Hot polymerization collection on appearance or the focus of focus is effectively suppressed.CN00122609.6 provides a kind of PROPENE IN GAS PHASE OXIDATION to produce methacrylaldehyde and acrylic acid, use the oxide catalyst containing Mo-Bi-Fe compound, described catalyst is filled in multitubular reactor of fixed bed, and the method can generate methacrylaldehyde and acrylic acid with high stable yield in long-time.The method is characterized in that in the each tubular reactor that configures vertically two or more reaction zones that each district's filling different catalysts is filled out catalyst Bi and/or Fe content and reduced with the ratio of Mo content from gas access end to gas outlet end.US2009415167A discloses a kind of method of producing unsaturated aldehyde and unsaturated acids, in reactor, pack two or more catalyst layer into, each catalyst layer by different holes density and or aperture size the catalyst of catalytic active component moulding fill, increase gradually from reactor inlet to the particular table area of outlet catalytic active component with control hole density and or aperture size, and then inhibitory reaction focus.Even if CN200410007263.1 provides a kind of under the condition of formation focus, active, selective, the life-span is all good, demonstrate for a long time the catalyst of stability, and use the method for producing acrylic acid of this catalyst.Said catalyst is following general formula (1) Mo
av
bw
ccu
da
eb
fc
go
xrepresent.A is at least one that select from cobalt, nickel, iron, lead, bismuth, B is at least one that select from antimony, niobium, tin, C is at least one that select from silicon, aluminium, titanium, zirconium, a, b, c, d, e, f, g, x represent respectively the atomic ratio of Mo, V, W, Cu, A, B, C, O, when a=12,2≤b≤15,0 < c≤10,0 < d≤6,0 < e≤30,0≤f≤6,0≤g≤60, x serve as reasons each element the state of oxidation determine numerical value.This catalyst can not effectively suppress emerging of beds focus.Under higher focus condition, reaction unit requires to have a superpower resistance to elevated temperatures, and reaction later separation, to absorb process operations expense also very high.CN200410048021.7 discloses a kind of for carry out the O composite metallic oxide catalyst of selective oxidation reaction in gas phase containing the gas of unsaturated aldehyde and a kind of gas of molecule-containing keto, particularly relates to a kind of methacrylaldehyde or MAL vapor phase catalytic oxidation is produced the O composite metallic oxide catalyst of corresponding acrylic or methacrylic acid.Catalyst is by 1. molybdenum, vanadium, copper main active component and 2. requisite at least by the stable component of antimony and titanium and the composite oxides that 3. nickel, iron, silicon, aluminium, alkali metal, alkaline-earth metal form.Be 2. and 3. wherein can within the scope of 120 DEG C to 900 DEG C prepared by roasting composite oxides.This catalyst shows the permanent stability under high activity and good selectivity.CN 03121882.2 discloses a kind of compound multi-metal-oxide catalyst and preparation method, is specially adapted to methacrylaldehyde vapor phase catalytic oxidation acrylic acid processed, and its catalyst consists of Mo
av
bcu
cte
dx
1 ex
2 fx
3 gx
4 hx
5 io
x, X
1a kind of element that is at least selected from tungsten and niobium, X
2a kind of element that is at least selected from magnesium, calcium, strontium and barium, X
3a kind of element of chosen from Fe, cobalt and nickel at least, X
4a kind of element that is at least selected from silicon, aluminium and titanium, X
5it is a kind of element that is at least selected from antimony, tin and bismuth, catalyst at least contains molybdenum, vanadium and copper, adding necessary tellurium stablizes catalyst main active component molybdenum oxide and molybdic acid copper crystal again, in the time carrying out catalytic reaction, there is lasting high activity and high selectivity, delay catalyst because of the molybdenum inactivation causing that runs off.CN03148701.7 provides a kind of supported catalyst, and this catalyst carrier has multidimensional structure, with the self supporting type multidimensional carrier structure of preformed (as foam, overall structure, fabric or other) or comprise Nb
2o
5, cordierite, partially stabilized zirconia, ceramic fibre or its mixture carrier, in succession on described carrier deposition comprise any order at least one molybdenum-containing layer, at least one containing vanadium layer, at least one forms load carrier containing tellurium layer and at least one containing the carbon monoxide-olefin polymeric of X layer, after roasting supported catalyst.Be oxidized to unsaturated carboxylic acid for alkane and become unsaturated nitrile with ammoxidation of paraffins, enough conversion ratios are provided and are applicable to selective.
All there is a problem in the method that above-mentioned inhibition focus produces, the catalyst being filled in reaction tube has all been diluted with various forms from the inlet to the outlet, both after having made catalyst runs some cycles, active decline also can not change thinner ratio, catalyst also cannot provide higher activity again, not only loading, dismantle, separate, reclaim catalyst makes troubles, and can reduce the reactivity of catalyst, especially industrial long-term operation catalyst activity reduction is faster, affects catalyst life.Therefore, need to develop a kind of high activated catalyst that can effectively suppress focus, to meet industrial propylene high-speed, highly selective oxidation acrolein, acrylic acid needs.In addition, under hot conditions, in catalyst, part active component molybdenum loses because of distillation from catalyst surface.The washing away of mixed airflow such as methacrylaldehyde, air (oxygen), nitrogen and steam also can make the loss of active component in catalyst.For the loss that suppresses molybdenum distillation causes active decay, CN1121504, by mixing copper component and zirconium and/or Titanium and/or the Cerium with specified particle diameter and specific area, can suppress dissipation effect and the over reduction of molybdenum composition; The effect that CN1445020 adds a small amount of tellurium to play to stablize free molybdenum trioxide and molybdic acid copper crystal structure, sublimation and the over reduction of molybdenum suppress to some extent; CN1583261 is taking molybdenum, vanadium, copper, tungsten and/or niobium as key component, and the composite oxides or its hopcalite that form with other element form the loss that catalyst suppresses molybdenum.
The invention provides one for the acrylic acid Catalysts and its preparation method of methacrylaldehyde selective oxidation system, in acrolein oxidation process, can under low temperature, high-load condition, react.
Summary of the invention
The object of this invention is to provide a kind of methacrylaldehyde or MAL selective oxidation is produced compound multi-metal-oxide catalyst of corresponding unsaturated acids and preparation method thereof.Different from the method for above-mentioned reduction focus, the present invention makes catalyst granules have gradient difference from inside to exterior active combination of components substrate concentration, can effectively reduce reactor localized heat and gather, and suppresses emerging of focus.This catalyst has the feature of reactivity and selective height, good stability, long service life.
The present invention relates to a kind of compound multi-metal-oxide catalyst, the chief component of this catalyst is by general formula (I) expression below
Mo
aV
bW
cNi
dA
eB
fSi
gO
x(I)
Wherein: Mo is molybdenum, V is vanadium, and W is tungsten, and Ni is nickel, and A is at least one element being selected from copper, cobalt, manganese; B is at least one element in selected among zirconium, strontium, lanthanum, magnesium and titanium; Si is silicon, and silicon is the carrier adding, and O is oxygen; A, b, c, d, e, f, g represent respectively each element atomic ratio, and wherein, in the time that a=12 is benchmark, b is a number of 3～10, preferably 3～7; C is a number of 0.5～5, preferably 1～3; D is a number of 1～5, preferably 1.5～3; E is a number of 0～3, f is a number of 0～3, g is a number of 0.5～30, x is the numerical value being determined by the oxygen of each oxide, described compound multi-metal-oxide catalyst has multilayer structure, outer double-layer structure in, every layer of catalyst chief component is identical, but the total content difference of one or more in silica, aluminium oxide or carborundum, the total content of one or more in outer silica, aluminium oxide or carborundum is than the height of internal layer parent, in molar content, the each constituent content concentration ratio of catalyst outer layer internal layer parent is low.
Catalyst of the present invention is multilayer structure, mainly by add the materials such as different amount silica, aluminium oxide, carborundum to be achieved concentration difference at ectonexine, that is to say, the total content of one or more in outer silica, aluminium oxide or carborundum is higher than internal layer parent, in molar content, outer each constituent content is lower by 0.5～30% than this constituent content of internal layer, and preferably 0.5～18%.Catalyst inner layer of the present invention also can not add silicon.
Methacrylaldehyde selective oxidation acrylic acid processed is because reaction temperature is more than 270 DEG C, and long period is under such pyroreaction condition, and the active component molybdenum in catalyst is easy to run off because of distillation.Preferably copper of A in catalyst of the present invention, B is strontium and/or lanthanum, strontium can regulate catalyst surface acidity, general formula for chief component (II) expression of catalyst, wherein e is a number of 0.5～3, f is a number of 0.05～3.Lanthanum and molybdenum, nickel, copper etc. can form stable crystal phase structure, are conducive to suppress part active component molybdenum and lose because of distillation from catalyst surface, and before and after catalyst reaction, active component molybdenum content is substantially constant, delays active deterioration rate, and catalyst stability is good.
Mo
aV
bW
cNi
dCu
eB
fSi
gO
x(II)
In catalyst of the present invention, active component comprises Mo, V, W, Ni, also can add one or more in cobalt, manganese, zirconium, strontium, magnesium and titanium, be conducive to improve dispersiveness and the tack of active component on the carriers such as silica, and then improve the selective of catalyst.In catalyst composition general formula (I), e is a number of 0.1～2, and f is a number of 0.05～2.The catalyst granules that the present invention has multilayer structure reduces successively from inside to exterior active combination of components substrate concentration, effectively reduce single tube reactor localized heat and gather, suppress emerging of focus, catalyst is easy-sintering not, reactivity is stable, can bear long period steady running.
The present invention has double-decker, and internal layer also can be called internal layer parent.
Compound multi-metal-oxide catalyst of the present invention adopts common preparation method, as adopted following step preparation.
First, Kaolinite Preparation of Catalyst internal layer parent:
By A in the compound that contains Mo, V, W, Ni and general formula (I)
eb
fthe each elemental constituent compound relating to dissolve and mix, carry out forming internal layer parent slurries after co-precipitation, dry, moulding, roasting obtains catalyst inner layer parent;
Secondly, method according to Kaolinite Preparation of Catalyst internal layer parent slurries is prepared outer layer catalyst slurries, in outer layer catalyst slurries preparation process, add one or more of the materials such as silica, aluminium oxide, carborundum, make in outer layer catalyst slurries each concentration of element lower than the concentration of this element of internal layer;
Finally, the outer layer catalyst of preparation is coated on catalyst inner layer parent successively, after roasting, obtains finished catalyst.
The present invention also can adopt a kind of multi-metal-oxide catalyst (III), and chief component is represented by following formula (III): Mo
av
bni
ccu
dnb
esr
fm
gn
hsi
io
x(III), wherein: Mo is molybdenum, V is vanadium, and Ni is nickel, and Cu is copper, and Nb is niobium, and Sr is strontium, and M is at least one element being selected from cobalt, iron, manganese, N is at least one element being selected from zinc, lanthanum, magnesium and boron, O is oxygen, Si is silicon, silicon is the carrier adding, a, b, c, d, e, f, g, h, i represents respectively each element atomic ratio, wherein in the time that a=12 is benchmark, b is a number of 3～8, c is a number of 0.5～6, d is a number of 0.5～3, e is a number of 0.05～2, f is a number of 0.05～1.5, g is a number of 0.05～2, h is a number of 0.05～1.5, i is a number of 0.5～10, x is the numerical value being determined by the oxygen of each oxide, described compound multi-metal-oxide catalyst has multilayer structure, outer double-layer structure in, every layer of catalyst chief component is identical, but silica, the total content difference of one or more in aluminium oxide or carborundum, outer silica, the total content of one or more in aluminium oxide or carborundum is than the height of internal layer parent, in molar content, the each constituent content concentration ratio of catalyst outer layer internal layer parent is low.In molar content, outer each constituent content is lower by 0.5～30% than this constituent content of internal layer.The preferred lanthanum of N in formula (III), lanthanum and nickel, copper etc. can form stable crystal phase structure, being conducive to suppress part active component molybdenum loses because of distillation from catalyst surface, before and after catalyst reaction, active component molybdenum content is substantially constant, delay active deterioration rate, catalyst activity and good stability.
The present invention can also adopt a kind of multi-metal-oxide catalyst (IV), and chief component is represented by following formula (IV): Mo
av
bw
cni
dsb
ea
fb
gsi
io
x(IV) wherein: wherein: Mo is molybdenum, V is vanadium, and W is tungsten, and Ni is nickel, and Sb is antimony, and Si is silicon, and silicon is the carrier adding, and A is at least one element being selected from strontium, iron, bismuth, B is at least one element in selected among zirconium, lanthanum, magnesium and phosphorus, O is oxygen, a, b, c, d, e, f, g, i represents respectively each element atomic ratio, wherein in the time that a=12 is benchmark, b is a number of 1～6, c is a number of 0.5～5, d is a number of 0.5～5, e is a number of 0.05～2, f is a number of 0.05～2, g is a number of 0.05～2, i is a number of 0.5～10, x is the numerical value being determined by the oxygen of each oxide, described compound multi-metal-oxide catalyst has multilayer structure, outer double-layer structure in, every layer of catalyst chief component is identical, but silica, the total content difference of one or more in aluminium oxide or carborundum, outer silica, the total content of one or more in aluminium oxide or carborundum is than the height of internal layer parent, in molar content, the each constituent content concentration ratio of catalyst outer layer internal layer parent is low.In molar content, outer each constituent content is lower by 0.5～35% than this constituent content of internal layer, and preferably 1～25%.(IV) the preferred lanthanum of B in, lanthanum and antimony, nickel etc. can form stable crystal phase structure, being conducive to suppress part active component molybdenum loses because of distillation from catalyst surface, before and after catalyst reaction, active component molybdenum content is substantially constant, delay active deterioration rate, catalyst activity and good stability.
The present invention can also use a kind of multi-metal-oxide catalyst (V), and chief component is represented by following formula (V): Mo
av
bcu
cce
da
gb
hsi
io
x(V) wherein: Mo is molybdenum, V is vanadium, and Cu is copper, and Ce is cerium, and Si is silicon, and silicon is the carrier adding, and A is at least one element being selected from strontium, antimony, tungsten, nickel, B is at least one element being selected from lanthanum, magnesium and phosphorus, O is oxygen, a, b, c, d, g, h represents respectively each element atomic ratio, wherein in the time that a=12 is benchmark, b is a number of 1～6, c is a number of 0.5～4, d is a number of 0.05～3, g is a number of 0～2, h is a number of 0～2, i is a number of 0.5～10, x is the numerical value being determined by the oxygen of each oxide, described compound multi-metal-oxide catalyst has multilayer structure, outer double-layer structure in, every layer of catalyst chief component is identical, but silica, the total content difference of one or more in aluminium oxide or carborundum, outer silica, the total content of one or more in aluminium oxide or carborundum is than the height of internal layer parent, in molar content, the each constituent content concentration ratio of catalyst outer layer internal layer parent is low.In molar content, outer each constituent content is lower by 0.5～35% than this constituent content of internal layer, and preferably 1～25%.Component cerium is conducive to component molybdenum, vanadium, the high degree of dispersion of copper on carrier silica, thereby improve the utilization rate of active component, but the addition of cerium is unsuitable too high, too high and vanadium, copper are competed molybdenum, activity declines on the contrary, meets (b+c)/d > 5.The preferred tungsten of A and/or nickel in formula (V), the preferred lanthanum of B, g is a number of 0.05～2, h is a number of 0.05～2, lanthanum and nickel, copper etc. can form stable crystal phase structure, are conducive to suppress part active component molybdenum and lose because of distillation from catalyst surface, and before and after catalyst reaction, active component molybdenum content is substantially constant, delay active deterioration rate, catalyst activity and good stability.
Above-mentioned catalyst (III), (IV) and (V) adopt common preparation method, also can adopt above-mentioned preparation method's preparation.
Catalyst inner layer parent of the present invention after moulding and outer all need to be at 300～480 DEG C after coating roasting 3～10h, compare not the catalyst of roasting respectively, repeatedly roasting can improve activity and the stability of catalyst.Can be that open roasting can be also enclosed roasting, calcination atmosphere can be the inert gases such as helium, nitrogen, argon gas.Catalyst layer easily chaps when thick roasting very much, for fear of be full of cracks be preferably in apply after 55～125 DEG C of oven dry, and then roasting.The outer layer catalyst bed thickness that is coated on internal layer parent is 0.5～2.5mm, preferably 1.0～2mm.
The compound of each component of catalyst of the present invention can use nitrate, ammonium salt, sulfate, oxide, hydroxide, chloride, acetate of each element etc.
After catalyst inner layer parent slurries of the present invention are dried, conventionally preferably adopt the forming methods such as extrusion molding, granulating and forming, compression molding to be processed into spherical, hollow spheres, ellipticity, cylindric, hollow circuit cylinder etc., preferably hollow circuit cylinder or spherical.
When catalyst of the present invention applies, preferably use binding agent, make ectonexine catalyst bonding more firm.Under rolling condition, spray binding agent at internal layer parent and infiltrate surface, then the outer layer catalyst powder for preparing of spraying, also internal layer parent can be put into the outer layer catalyst slurries that the prepare coating of rolling.Binding agent is selected from one or more in water, alcohols or ethers.Alcohols is as ethanol, propyl alcohol, butanols; Ethers is as ether and butyl ether.
Preferably uneven, the rough surface of each layer of surface of catalyst of the present invention, is conducive to apply, and between ectonexine, bonding is more firm.
The present invention is in order to improve intensity, the efflorescence degree of catalyst, can in above-mentioned outer layer catalyst, add in glass fibre, graphite, pottery or various whisker one or more.
Catalyst of the present invention can directly use, and also can be carried on inert carrier and use.Related inert carrier can be one or more mixture of aluminium oxide, silica, carborundum etc.
The present invention also provides a kind of methacrylaldehyde selective oxidation acrylic acid processed: adopt fixed bed single tube reactor; Reaction raw materials methacrylaldehyde, water, air more than 180 DEG C enter reactor after preheating through preheater, salt bath heating, and reaction process condition is: 245～265 DEG C of salt temperatures, preferably 250～262 DEG C; Air speed 1400～2500h
-1, preferably 1500～2000h
-1, feed composition: methacrylaldehyde 7～12 volume %, steam 11～18%, air 10～18 volume %, nitrogen 60～72 volume %; In reactor, be equipped with above-mentioned catalyst (III), (IV) or (V) in one or more.Acrolein conversion rate is between 98.2～99.5%, and acrylic acid is selectively between 88.0～91.3%.Hot(test)-spot temperature is between 279～291.
Because catalyst initial reaction activity is very high, thus on single tube reactor bed, be easy to produce focus or produce heat localization, the easy sintering of catalyst, this loses concerning suitability for industrialized production methacrylaldehyde acrylic acid is very serious.In raw material, pass into a certain amount of steam, because specific heat of water is large, can take away a large amount of reaction heat, make active decline but steam input greatly often makes catalyst member active component solution-off.The present invention has the compound multi-metal-oxide catalyst of multilayer structure by preparation, make catalyst granules have gradient difference from inside to exterior active combination of components substrate concentration, and the every outer active component concentration of catalyst is lower than its adjacent inner layer active component concentration, like this, under high-speed reaction condition, because the active component concentration of catalyst outer surface is low, so corresponding activity is also low, therefore can effectively suppress emerging of focus and gathering of heat, reduce the growing amount of accessory substance (as hydrocarbon), improve the selective of object product.Double-deck catalyst has good water repelling property.And when after catalyst runs a period of time, catalyst has release effects, under mixed airflow washes away, even if catalyst surface active component has part to run off, but because internal layer catalyst active component concentration is higher, can play supplementary effect, so can keep catalyst activity lasting stability.
Evaluating catalyst performance indications are defined as follows:
Molal quantity × 100% of methacrylaldehyde in the total mole number/raw material of acrolein conversion rate (%)=acrolein reaction
Selective (the %)=methacrylaldehyde of acrylic acid is converted into total mole number × 100% of acrylic acid molal quantity/acrolein reaction
Detailed description of the invention
With specific embodiment, compound multi-metal-oxide catalyst and preparation method thereof is described below, and this catalyst prepares the catalytic performance in acrylic acid at methacrylaldehyde selective oxidation, but scope of the present invention is not limited to these embodiment.
Embodiment 1:
The preparation of catalyst 1
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active component slurries (a)
Under stirring condition, get 24.6 grams of 148 grams of ammonium molybdates, ammonium metavanadates, be dissolved in (water temperature is more than 65 DEG C) in 500ml pure water, obtain slurries (1), then get 64 grams of ammonium paratungstates, 5.5 grams of strontium nitrates, 17.9 grams of copper nitrates, 10.2 grams of cobalt nitrates and be dissolved in (water temperature is more than 65 DEG C) in 500ml pure water, fully be uniformly mixed, obtain slurries (2).Then, slurries (1) mix with slurries (2), obtain slurries (3), obtain active component slurries (a).
(2) preparation of catalyst inner layer parent
In active component slurries (a), add 4.2 grams of silica, 80 DEG C of strong stirrings carry out heat drying after coprecipitation reaction for 3 hours, in nitrogen with 160 DEG C of heat treatments 3 hours, then be the hollow columnar particle of φ 4.5 × 5mm through banded extruder extrusion modling, dry rear 450 DEG C of roastings 5 hours for 110 DEG C, make catalyst Precursors, this catalyst inner layer parent consists of: Mo
12v
3w
3.5ni
4cu
1.1co
0.5sr
0.3si
1
Step 2: Kaolinite Preparation of Catalyst skin
(1) preparation of active component slurries (a)
Preparation with active component slurries (a) in embodiment 1 catalyst inner layer parent is identical.
(2) preparation of catalyst outer layer
Active component slurries (a) and 45 grams of silicon dioxide powders are carried out to coprecipitation reaction heat drying after 2.5 hours, in nitrogen with 150 DEG C of heat treatments 3 hours, then 500 DEG C of roastings 4 hours, process to obtain catalyst outer layer powder through pulverizing, grind, sieving.
Step 3: Kaolinite Preparation of Catalyst 1
Catalyst inner layer parent prepared by step 1 is placed in round bottom container, under container rotation condition, spray ethanolic solution to catalyst Precursors, under the condition of fully wetting catalyst inner layer parent, stop operating, put it into rapidly in the round bottom container of outer layer catalyst powder that is placed with step 2 gained of another rotation, apply, coating layer thickness, at 1.0～2.0mm, obtains catalyst 1 for 4.5 hours through 450 DEG C of roastings after 105 DEG C of oven dry of gained catalyst.
Comparative example 1:
Taking the internal layer parent of catalyst 1 as comparative catalyst 1, banded extruder extrusion modling is the hollow columnar particle of φ 5 × 5mm, and reaction condition is with the appreciation condition of catalyst 1.
Comparative example 2:
Taking the skin of catalyst 1 as comparative catalyst 2, banded extruder extrusion modling is the hollow columnar particle of φ 5 × 5mm, and reaction condition is with the appreciation condition of catalyst 1.
Embodiment 2:
The preparation of catalyst 2
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active component slurries (a)
Under stirring condition, get 40.9 grams of 148 grams of ammonium molybdates, ammonium metavanadates, be dissolved in (water temperature is more than 65 DEG C) in 500ml pure water, obtain slurries (1), then get 54.8 grams of ammonium paratungstates, 61 grams of nickel nitrates are dissolved in (water temperature is more than 65 DEG C) in 500ml pure water, fully be uniformly mixed, obtain slurries (2).Then, slurries (1) mix with slurries (2), obtain slurries (3), obtain active component slurries (a).
(2) preparation of catalyst Precursors
In slurries (a), add 5 grams of silica, 80 DEG C of strong stirrings carry out heat drying after coprecipitation reaction for 2 hours, in nitrogen with 160 DEG C of heat treatments 3 hours, then be the hollow columnar particle of φ 4.5 × 5mm through banded extruder extrusion modling, dry rear 450 DEG C of roastings 4 hours for 60 DEG C, make catalyst Precursors, this catalyst Precursors consists of: Mo
12v
5w
3ni
3
Step 2: Kaolinite Preparation of Catalyst skin
(1) preparation of active component slurries (a)
Preparation with active component slurries (a) in embodiment 2 catalyst inner layer parents is identical.
(2) preparation of catalyst outer layer
Active component slurries (a) and 14 grams of silicon dioxide powders and 4 grams of graphite are carried out answering after co-precipitation heat drying after 50 minutes, in nitrogen with 160 DEG C of heat treatments 3 hours, then 500 DEG C of roastings 4 hours, process to obtain catalyst outer layer powder through pulverizing, grind, sieving.
Step 3: Kaolinite Preparation of Catalyst 2
Catalyst inner layer parent prepared by step 1 is placed in round bottom container, under container rotation condition, spray ethanolic solution to catalyst Precursors, fully wetting catalyst inner layer parent, put it into rapidly in the round bottom container of the catalyst outer layer that is placed with step 2 gained of another rotation, apply, coating layer thickness is in the time of 0.8～1.0mm, taking-up internal layer parent is put into another round bottom container rotation and is sprayed ethanolic solution after one to two minute again, then put into the round bottom container continuation coating that catalyst outer layer is housed, until coating layer thickness stops applying in the time of 1.5～2.0mm, gained catalyst obtains catalyst 2 for 3 hours through 500 DEG C of roastings after drying.
Comparative example 3:
Taking the internal layer parent of catalyst 2 as comparative catalyst 3, banded extruder extrusion modling is the hollow columnar particle of φ 5 × 5mm, and reaction condition is with the appreciation condition of catalyst 1.
Comparative example 4:
Taking the skin of catalyst 2 as comparative catalyst 4, banded extruder extrusion modling is the hollow columnar particle of φ 5 × 5mm, and reaction condition is with the appreciation condition of catalyst 1.
Embodiment 3:
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active component slurries (a)
Under stirring condition, get 148 grams of ammonium molybdates, 24.6 ammonium metavanadates gram, be dissolved in (water temperature is more than 65 DEG C) in 500ml pure water, obtain slurries (1), then get 18.3 grams of ammonium paratungstates, 21.2 copper nitrates, 40.7 grams of nickel nitrates and be dissolved in (water temperature is more than 65 DEG C) in 500ml pure water, fully be uniformly mixed, obtain slurries (2).Then, slurries (1) mix with slurries (2), obtain slurries (3), obtain active component slurries (a).
(2) preparation of catalyst inner layer parent
In slurries (a), add 8.4 grams of silica, 80 DEG C of strong stirrings carry out heat drying after coprecipitation reaction for 3 hours, in nitrogen with 160 DEG C of heat treatments 3 hours, then be the hollow columnar particle of φ 4.5 × 5mm through banded extruder extrusion modling, dry rear 350 DEG C of roastings 8 hours, make catalyst Precursors, this catalyst inner layer parent consists of: Mo
12v
3w
1ni
2cu
1.3
Step 2: Kaolinite Preparation of Catalyst skin
(1) preparation of active component slurries (a)
With preparation and raw materials used identical (following examples are identical) of active component slurries (a) in embodiment 3 catalyst inner layer parents.
(2) preparation of catalyst outer layer
Active component slurries (a) and 7.8 grams of silicon dioxide powders and 5.7 grams of aluminium oxide are carried out answering after co-precipitation heat drying after 50 minutes, in nitrogen with 160 DEG C of heat treatments 3 hours, then 400 DEG C of roastings 5 hours, process to obtain catalyst outer layer powder through pulverizing, grind, sieving.
Step 3: Kaolinite Preparation of Catalyst 3
Catalyst inner layer parent prepared by step 1 is placed in round bottom container, under container rotation condition, spray diethyl ether solution to catalyst Precursors, under the condition of fully wetting catalyst inner layer parent, stop operating, put it into rapidly in the round bottom container of the catalyst outer layer that is placed with step 2 gained of another rotation, apply, coating layer thickness, at 1.5～2.0mm, obtains catalyst 3 for 4 hours through 450 DEG C of roastings after 85 DEG C of oven dry of gained catalyst.
Comparative example 5:
Taking the internal layer parent of catalyst 3 as comparative catalyst 5, be then the hollow columnar particle of φ 5 × 5mm through banded extruder extrusion modling, reaction condition is with the appreciation condition of catalyst 1.
Embodiment 4:
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active component slurries (a)
Under stirring condition, get 148 grams of ammonium molybdates, 57.3 ammonium metavanadates gram, be dissolved in (water temperature is more than 65 DEG C) in 500ml pure water, obtain slurries (1), then get 36.6 grams of ammonium paratungstates, 14.6 strontium nitrates, 30.5 grams of nickel nitrates and be dissolved in (water temperature is more than 65 DEG C) in 500ml pure water, add again 5.6 grams of titanium dioxide, be fully uniformly mixed, obtain slurries (2).Then, slurries (1) mix with slurries (2), obtain slurries (3), obtain active component slurries (a).
(2) preparation of catalyst inner layer parent
In slurries (a), add 6.5 grams of silica, 80 DEG C of strong stirrings carry out heat drying after coprecipitation reaction for 3 hours, in nitrogen with 160 DEG C of heat treatments 3 hours, then be the hollow columnar particle of φ 4.5 × 5mm through banded extruder extrusion modling, dry rear 350 DEG C of roastings 8 hours for 120 DEG C, make catalyst Precursors, this catalyst inner layer parent consists of: Mo
12v
7w
2ni
1.5sr
0.8ti
1.0
Step 2: Kaolinite Preparation of Catalyst skin
With preparation method and raw materials used identical (following examples are identical) of embodiment 4 catalyst outer layer, just add 6.3 grams of silica and 20 grams of carborundum.
Step 3: Kaolinite Preparation of Catalyst 4
Catalyst inner layer parent prepared by step 1 is placed in round bottom container, under container rotation condition, spray ethanolic solution to catalyst, under the condition of fully wetting catalyst inner layer parent, spray the outer layer catalyst powder of step 2 gained, apply, coating layer thickness, at 0.8～1.5mm, obtains catalyst 4 for 5 hours through 450 DEG C of roastings after 80 DEG C of oven dry of gained catalyst.
Comparative example 6:
Taking the internal layer catalyst of catalyst 4 as comparative catalyst 6,300 DEG C of roastings 2.5 hours, be the hollow columnar particle of φ 5 × 5mm through banded extruder extrusion modling, reaction condition is with the appreciation condition of catalyst 1.
Embodiment 5:
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active component slurries (a)
Under stirring condition, get 148 grams of ammonium molybdates, 73.7 ammonium metavanadates gram, be dissolved in (water temperature is more than 65 DEG C) in 500ml pure water, obtain slurries (1), then get 82.3 grams of ammonium paratungstates, 14.6 grams of strontium nitrates, 29.3 grams of copper nitrates, 3.5 grams of potassium nitrate, 16.8 grams of magnesium nitrates, 20.4 grams of nickel nitrates and be dissolved in (water temperature is more than 65 DEG C) in 500ml pure water, fully be uniformly mixed, obtain slurries (2).Then, slurries (1) mix with slurries (2), obtain slurries (3), obtain active component slurries (a).
(2) preparation of catalyst inner layer parent
In slurries (a), add 12.6 grams of silica, 80 DEG C of strong stirrings carry out heat drying after coprecipitation reaction for 3 hours, in nitrogen with 160 DEG C of heat treatments 3 hours, then be the hollow columnar particle of φ 4.5 × 5mm through banded extruder extrusion modling, dry rear 480 DEG C of roastings 4 hours for 120 DEG C, make catalyst Precursors, this catalyst inner layer parent consists of: Mo
12v
9w
4.5ni
1cu
1.8k
0.5mg
1.3
Step 2: Kaolinite Preparation of Catalyst skin
Preparation with embodiment 5 catalyst outer layer is identical, just adds 9.7 grams of silica, 6 grams of graphite and 36 grams of aluminium oxide.
Step 3: Kaolinite Preparation of Catalyst 5
Catalyst inner layer parent prepared by step 1 is placed in round bottom container, under container rotation condition, spray distilled water to catalyst Precursors, under the condition of fully wetting catalyst inner layer parent, spray the outer layer catalyst powder of step 2 gained, apply, coating layer thickness, at 0.8～1.2mm, obtains catalyst 5 for 6 hours through 450 DEG C of roastings after 75 DEG C of oven dry of gained catalyst.
Comparative example 7:
Taking the internal layer catalyst of catalyst 5 as comparative catalyst 7, be then the hollow columnar particle of φ 5 × 5mm through banded extruder extrusion modling, reaction condition is with the appreciation condition of catalyst 1.
Embodiment 6
Preparation process and raw material with embodiment 5 catalyst 5 are identical, just add 13.6 grams of lanthanum nitrates and 5.5 grams of strontium nitrates, and internal layer adds 7.3 grams of silica; Skin adds 10.4 grams of silica.Catalyst 6 internal layer parents consist of: Mo
12v
5w
0.7ni
2.8cu
0.8sr
0.3la
0.6
Oxidation reaction
Fixed bed single tube reactor internal diameter 25mm, inside establishes thermocouple, and reactor packs the above-mentioned catalyst of 45ml, salt bath heating into.From above-mentioned reaction tube porch with air speed 1400h
-1import the mist of methacrylaldehyde 9 volume %, air 12 volume %, steam 14 volume %, nitrogen 65 volume %.The performance of catalyst as shown in Table 1 and Table 2.The difficult losses such as catalyst effectively suppresses focus, active component molybdenum, before and after catalyst reaction, molybdenum equal size is substantially constant, and catalyst catalytic performance is stable, reacts 1000 hours rear catalysts and substantially can reach fresh catalyst activity level, and catalyst stability is good.Comparative example 1～7 catalyst can not effectively suppress focus, and poor selectivity is reacted after 1000 hours rear catalysts activity under the washing away of the mixed airflows such as steam and obviously declined.
Table 1 reacts 20 hours post-evaluation results
Table 2 reacts 1000 hours post-evaluation results
Claims (15)
1. a compound multi-metal-oxide catalyst, is characterized in that the chief component of this catalyst is by below
General formula (I) represents Mo
av
bw
cni
da
eb
fsi
go
x(I)
Wherein: Mo is molybdenum, V is vanadium, and W is tungsten, and Ni is nickel, and A is at least one element being selected from copper, cobalt, manganese, B is at least one element in selected among zirconium, strontium, lanthanum, magnesium and titanium, Si is silicon, and silicon is the carrier adding, and O is oxygen, a, b, c, d, e, f, g represents respectively each element atomic ratio, wherein in the time that a=12 is benchmark, b is a number of 3～10, c is a number of 0.5～5, d is a number of 1～5, e is a number of 0～3, f is a number of 0～3, g is a number of 0.5～30, x is the numerical value being determined by the oxygen of each oxide, described compound multi-metal-oxide catalyst has interior outer double-layer structure, the total content of one or more in outer silica or carborundum is than the height of internal layer parent, in molar content, the each constituent content concentration ratio of catalyst outer layer internal layer parent is low.
2. catalyst according to claim 1, is characterized in that b is a number of 3～7.
3. catalyst according to claim 1, is characterized in that c is a number of 1～3.
4. catalyst according to claim 1, is characterized in that d is a number of 1.5～3.
5. catalyst according to claim 1, is characterized in that A is copper, and the composition of catalyst represents Mo by (II)
av
bw
cni
dcu
eb
fsi
go
x(II) wherein e is a number of 0.1～2.
6. catalyst according to claim 5, is characterized in that B is strontium and/or lanthanum, and wherein f is a number of 0.05～2.
7. catalyst according to claim 1, is characterized in that catalyst is double-decker, and in molar content, outer each constituent content is lower by 0.5～30% than this constituent content of internal layer.
8. catalyst according to claim 1, is characterized in that the each constituent content of catalyst outer layer is lower by 0.5～10% than this constituent content of adjacent inner layer.
9. catalyst according to claim 1, is characterized in that A is at least one element being selected from copper, cobalt, manganese; B is at least one element in selected among zirconium, strontium, magnesium and titanium; In catalyst composition general formula (I), e is a number of 0.1～2, and f is a number of 0.05～2.
10. according to the preparation method of the catalyst described in claim 1～9 any one, it is characterized in that comprising the steps:
First, Kaolinite Preparation of Catalyst internal layer parent:
By A in the compound that contains Mo, V, W, Ni and general formula (I)
eb
fthe each elemental constituent compound relating to dissolve and mix, carry out forming internal layer parent slurries after co-precipitation, dry, moulding, roasting obtains catalyst inner layer parent;
Secondly, prepare outer layer catalyst slurries according to the method for Kaolinite Preparation of Catalyst internal layer parent slurries, in outer layer catalyst slurries preparation process, add one or more of silica, silicon carbide species;
Finally, the outer layer catalyst of preparation is coated on catalyst inner layer parent successively, after roasting, obtains finished catalyst.
The preparation method of 11. catalyst according to claim 10, it is characterized in that internal layer parent after moulding and outer after coating at 300～480 DEG C roasting 3～10h, adopt open roasting or enclosed roasting, calcination atmosphere is helium, nitrogen or argon gas.
The preparation method of 12. catalyst as claimed in claim 10, is characterized in that when described catalyst applies using binding agent, binding agent to be selected from one or more in water, Ludox, aluminium colloidal sol.
The preparation method of 13. catalyst as claimed in claim 10, is characterized in that when described catalyst applies using binding agent, binding agent to be selected from one or more in alcohols or ethers.
14. catalyst as described in claim 1～9 any one, it is characterized in that adding glass fibre, graphite, pottery or whisker in each layer of catalyst in one or more.
15. 1 kinds of multi-metal-oxide catalysts, is characterized in that catalyst chief component is represented by following formula (III): Mo
av
bni
ccu
dnb
esr
fm
gn
hsi
io
x(III), wherein: Mo is molybdenum, V is vanadium, and Ni is nickel, and Cu is copper, and Nb is niobium, and Sr is strontium, and M is at least one element being selected from cobalt, iron, manganese, N is at least one element being selected from zinc, lanthanum, magnesium and boron, O is oxygen, Si is silicon, silicon is the carrier adding, a, b, c, d, e, f, g, h, i represents respectively each element atomic ratio, wherein in the time that a=12 is benchmark, b is a number of 3～8, c is a number of 0.5～6, d is a number of 0.5～3, e is a number of 0.05～2, f is a number of 0.05～1.5, g is a number of 0.05～2, h is a number of 0.05～1.5, i is a number of 0.5～10, x is the numerical value being determined by the oxygen of each oxide, described multi-metal-oxide catalyst has interior outer double-layer structure, every layer of catalyst chief component is identical, but silica, the total content difference of one or more in aluminium oxide or carborundum, outer silica, the total content of one or more in aluminium oxide or carborundum is than the height of internal layer parent, in molar content, the each constituent content concentration ratio of catalyst outer layer internal layer parent is low, in molar content, outer each constituent content is lower by 0.5～30% than this constituent content of internal layer.
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| CN101992093A (en) * | 2010-09-28 | 2011-03-30 | 上海华谊丙烯酸有限公司 | Preparation method of catalyst for preparing unsaturated aldehyde and unsaturated acid in high selectivity |
| CN102091634A (en) * | 2010-12-13 | 2011-06-15 | 上海华谊丙烯酸有限公司 | Preparation method of catalyst used in reaction of preparing methylacrolein by selective oxidation of isobutene/tertiary butanol |
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| CN101992093A (en) * | 2010-09-28 | 2011-03-30 | 上海华谊丙烯酸有限公司 | Preparation method of catalyst for preparing unsaturated aldehyde and unsaturated acid in high selectivity |
| CN102091634A (en) * | 2010-12-13 | 2011-06-15 | 上海华谊丙烯酸有限公司 | Preparation method of catalyst used in reaction of preparing methylacrolein by selective oxidation of isobutene/tertiary butanol |
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