CN106732634A - One kind is used to produce the catalyst and preparation method of unsaturated aldehyde (acid) - Google Patents
One kind is used to produce the catalyst and preparation method of unsaturated aldehyde (acid) Download PDFInfo
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- CN106732634A CN106732634A CN201611070215.6A CN201611070215A CN106732634A CN 106732634 A CN106732634 A CN 106732634A CN 201611070215 A CN201611070215 A CN 201611070215A CN 106732634 A CN106732634 A CN 106732634A
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- Prior art keywords
- catalyst
- powder
- heat transfer
- transfer medium
- acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 239000002253 acid Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract 5
- 239000000843 powder Substances 0.000 claims abstract description 58
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000012546 transfer Methods 0.000 claims abstract description 41
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 238000004108 freeze drying Methods 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001336 alkenes Chemical class 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 37
- 239000002002 slurry Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 239000012018 catalyst precursor Substances 0.000 claims description 11
- 229910045601 alloy Inorganic materials 0.000 claims description 10
- 239000000956 alloy Substances 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052790 beryllium Inorganic materials 0.000 claims description 4
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229920002522 Wood fibre Polymers 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229920000084 Gum arabic Polymers 0.000 claims description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 241000978776 Senegalia senegal Species 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000205 acacia gum Substances 0.000 claims description 2
- 235000010489 acacia gum Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 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 compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims 1
- 238000005253 cladding Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 238000012360 testing method Methods 0.000 abstract description 12
- 239000001282 iso-butane Substances 0.000 abstract description 2
- 235000013847 iso-butane Nutrition 0.000 abstract description 2
- -1 iso-butane alkene Chemical class 0.000 abstract description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N trimethylmethane Natural products CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract 1
- 229910052797 bismuth Inorganic materials 0.000 abstract 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical class 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 229910052750 molybdenum Inorganic materials 0.000 abstract 1
- 239000011733 molybdenum Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 150000001299 aldehydes Chemical class 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000008246 gaseous mixture Substances 0.000 description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material 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
- 229910019614 (NH4)6 Mo7 O24.4H2 O Inorganic materials 0.000 description 1
- 229910001339 C alloy Inorganic materials 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910003206 NH4VO3 Inorganic materials 0.000 description 1
- 230000010802 Oxidation-Reduction Activity Effects 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- WXYNCCWBUXKSBG-UHFFFAOYSA-N copper;nitric acid Chemical compound [Cu].O[N+]([O-])=O WXYNCCWBUXKSBG-UHFFFAOYSA-N 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical group Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8877—Vanadium, tantalum, niobium or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
It is used to produce the catalyst and preparation method of unsaturated aldehyde (acid) the present invention relates to one kind.The catalyst includes active component and heat transfer medium.Active component is the oxide or composite oxides of the metals such as molybdenum, bismuth, iron, and heat transfer medium is the metal powder or alloyed powder of coated with silica, with excellent heat conductivility.Catalyst preparation process uses freeze-drying mode simultaneously, and calcination atmosphere is the mixed gas that oxygen and a kind of inert gas are constituted according to a certain percentage.During by the catalyst for being catalyzed the strong exothermal reaction of unsaturated olefin oxidation generation unsaturated aldehyde (acid), particularly preparing MAL (acid) for catalyzing iso-butane alkene, the problem that hot localised points temperature will not be produced too high, under relatively low hot(test)-spot temperature, excellent ethylenic unsaturation hydrocarbon conversion rate and unsaturated aldehyde (acid) selectivity is shown.
Description
Technical field
The invention belongs to catalyst field, it is related to a kind of catalyst with high thermal conductivity and preparation method thereof, also relates to
And application of the catalyst in production unsaturated aldehyde (acid).
Background technology
Unsaturated olefin oxidation generation unsaturated aldehyde (acid) is strong exothermal reaction, and the short time can release largely in startup procedure
Heat, heat causes hot localised points too high in the party of reactor inner product, reduces the selectivity of target product, or even can burn reaction
Device, triggers fused salt leakage, and the accident such as cause to stop or explode.Therefore, in order to realize safety in production, while improving target product
Yield, catalyst need to have good heat-transfer capability and excellent selectivity.
Chinese patent CN1089081C is proposed the catalyst with differential responses activity, according to order from low to high,
From reactor feedstocks gas entrance to outlet, load successively to suppress the aggregation of heat, but the method substantially increases catalyst
Production cost, the filling to catalyst in large-scale reactor can cause very big inconvenience.Chinese patent
Be coated on for active component coated catalyst be obtained on inert carrier ball by CN1270824C, carries out removing heat beneficial to carrier ball.But
Coated catalyst is higher to abrasion strength resistance requirement, and bed pressure drop is larger.Chinese patent CN101385978B proposes urging
The preferable material of some thermal conductive properties (such as silica flour, germanium powder, graphite), and compression molding are added in agent preparation process, in phase
Under same hot(test)-spot temperature, after adding conduction material, the isobutene conversion and MAL of catalyst have selectively changed
It is kind, but the patent reports that heat-conducting medium heat-transfer capability is limited, and its catalyst activity still has larger difference with industrial production demand
Away from, it is necessary to further improve the catalyst capacity of heat transmission, reduction hot(test)-spot temperature, while keeping isobutene conversion and methyl higher
Acrolein selectivity.
The reaction network of unsaturated olefin oxidation generation unsaturated aldehyde (acid) is more complicated, and the active sites being related to have acid work
Property center, oxidation-reduction activities center.Wherein easily there is deep oxidation reaction in alkene intermediates on acidic site, generate small
The aldehyde of molecule, acid, COx, so that reaction system thermal discharge is greatly increased, selectivity declines.Catalyst for catalytic oxidation needs to close
Suitable acid centre, could fundamentally improve target product selectivity, thermal discharge be reduced, while needing catalyst to possess well
Heat-transfer capability, suppress hot localised points generation, this be olefine selective catalyst for catalytic oxidation exploitation difficult point.
The content of the invention
An object of the present invention is：A kind of catalyst is provided, the catalyst has a kind of heat transfer medium of cladded type,
The heat transfer medium has excellent heat conductivility, is highly suitable for the shifting heat of strong exothermal reaction.The catalyst has preferable
Heat conductivility and catalysis activity, during for unsaturated olefin selective oxidation reaction, can in time shift reaction heat, will not produce
The too high problem of raw hot localised points temperature, while showing excellent conversion ratio and selectivity.
Another object of the present invention is to：The preparation method of above-mentioned cladded type heat transfer medium is provided, the preparation method has
Raw material sources extensively, process is simple, it is reproducible the characteristics of.
It is yet a further object of the present invention to provide the preparation method of Above-mentioned catalytic agent.
To achieve the above objectives, the present invention is adopted the following technical scheme that：
A kind of catalyst, the catalyst has below formula：
Mo12BiaFebCocCudCseVfOy/M
Wherein, a, b, c, d, e, f represent the atomic ratio of corresponding element, a=0.5~5, b=0.5~5, c=0.5 respectively
~5, d=0.02~1, e=0.2~1, f=0~3, y is the atomic ratio for meeting oxygen required for each element chemical valence；M is represented
Cladded type heat transfer medium, the cladded type heat transfer medium is coated with silica metal powder and/or coated with silica alloyed powder.
In catalyst of the invention, in the cladded type heat transfer medium, silica accounts for the 0.1- of heat transfer medium gross weight
1wt%.
In catalyst of the invention, in heat transfer medium, coating layer thickness of the silica on metal powder or alloyed powder surface is
0.1-50 μm, preferably 1-10 μm；The particle diameter of heat transfer medium is 50-1000 μm, is preferably 200-800 μm.
Metal powder or alloyed powder particle diameter and silicon oxide coating thickness need that the heat transfer medium of catalyst of the present invention is used
Want precise control.Diameter of particle is too small, coating is too thick, and catalyst heat transfer is limited by thermal resistance, is unfavorable for giving full play to metal
Excellent heat-transfer capability；Diameter of particle too big, coating is too thin, is unfavorable for shaping of catalyst, and influence heat transfer medium wear-resisting strong
Degree.
In catalyst of the invention, shared mass fraction is 5-50wt%, preferably 10- to heat transfer medium in the catalyst
30wt%.The heat transfer medium of too high amount can greatly increase catalyst cost, while active component content is reduced, influence reaction is lived
Property；The heat transfer medium for crossing low content is then not enough to withdraw unnecessary reaction heat in time, can still produce focus higher.
Catalyst of the invention, in the cladded type heat transfer medium by coated with silica be metal powder when, metal unit
Element is selected from least one in beryllium, aluminium, magnesium, nickel, iron, titanium, preferably aluminium；When by coated with silica be alloyed powder when, alloy
Metallic element be selected from least one in beryllium, aluminium, magnesium, nickel, iron, titanium, the nonmetalloid of alloy is selected from carbon, boron, silicon, phosphorus
At least one, the weight/mass percentage composition of nonmetalloid is 0.01%-5wt% in alloy.
Metal or alloy is excellent heat transfer medium, thermal conductivity factor typically in hundreds of W/ (mK) left and right, far above conventional
Heat conduction diluent, such as aluminum oxide, silica flour, ceramic fibre.Unsaturated olefin generates unsaturated aldehyde (acid) by catalysis oxidation
During, acids product can be generated, with metal or alloy reaction, cause target product to lose and destroyed with catalyst structure or even lose
It is living.The present invention, on metal powder or the surface of alloyed powder, catalyst is mixed and made into catalyst precursor using coated with silica,
The haptoreaction of acids product and metal or alloy is avoided, while there is good thermal conductivity by catalyst prepared by the present invention
Can, under relatively low hot(test)-spot temperature, show excellent isobutene conversion and MAL selectivity.
The preparation method of the heat transfer medium of catalyst of the present invention, comprises the following steps：
1) metal powder or alloyed powder are placed in ball grinder with the Ludox that mass concentration is 5%-50wt%, Ludox is dense
Degree is preferably 10-15wt%, and powder need to submerge in Ludox completely, and ball-milling medium is zirconia ball, and particle diameter is 2-3mm；
2) ball grinder is sealed, rolling ball milling 1-24h, preferably 5-10h obtain slurry；
3) by slurry in 1-12h, preferably 5-10h is dried at 100-150 DEG C, powder is obtained, the drying mode has baking oven
Electrical heating, infrared radiation heating, flash distillation, spray drying etc., preferably baking oven electrical drying；
4) powder is placed in Muffle furnace and is calcined, heating rate is 1-10 DEG C/min, is preferably 3-6 DEG C/min, roasting temperature
Spend is 800-1600 DEG C, preferably 1200-1400 DEG C, roasting time 2-4h.
The preparation method of catalyst of the present invention is comprised the following steps：
1. by the atomic ratio of each element composition, the water for containing Mo, Bi, Fe, Co, Cu, Cs, V element is dissolved with water or diluted acid
Dissolubility or acid-soluble compound, adjust pH=0.5~7, preferably pH=2~4, then 20~100 after being well mixed with ammoniacal liquor
DEG C, curing 1~15h, preferably 5-10h are stirred at a temperature of preferably 50-80 DEG C, obtain the slurry containing active component, by slurry-
Freeze-drying 4-16h at a temperature of 60~0 DEG C, then after 3~10h of preroast at a temperature of 400~550 DEG C, obtains catalyst powder
Body,
2. catalyst powder and the mixed-forming such as heat transfer medium and pore creating material, binding agent are obtained into catalyst precursor,
3. catalyst precursor is activated into 3~10h in 400~650 DEG C of roasting temperatures and obtains catalyst.
In the present invention, the water-soluble or acid-soluble compound containing Mo elements is ammonium heptamolybdate or molybdenum trioxide；Containing Bi
The water-soluble or acid-soluble compound of element is bismuth nitrate or bismuth oxide；Water-soluble or acid-soluble compound containing Fe elements
It is ferric nitrate, iron chloride, frerrous chloride, ferric acetyl acetonade, iron oxide or ferrous oxide, preferably ferric nitrate or iron chloride；Contain
The water-soluble or acid-soluble compound of Co elements is cobalt nitrate or cobalt chloride；Water-soluble or acid-soluble compound containing Cu elements is
Cupric oxide, copper nitrate, copper chloride, copper acetate, stannous chloride, acetylacetone copper, cupric oxalate or basic copper carbonate, preferably nitric acid
Copper, copper chloride or copper acetate；Water-soluble or acid-soluble compound containing Cs elements is cesium carbonate or cesium nitrate；Water containing V element
Dissolubility or acid-soluble compound are ammonium metavanadate or vanadic anhydride.
In the preparation method of catalyst of the present invention, the step 1. freeze-drying, selected from air freezing drying, vacuum refrigeration
Dry, atomizing freeze drying, preferably atomizing freeze drying.Control the operating parameter of drying machine so that catalyst powder particle diameter
It is 10-1000 μm, preferably 30-300 μm.Conventional drying pattern such as electrical heating drying, infrared heating are in drying process to slurry
The heating operation of material, can trigger the migration of active component；The dry inlet temperature of atomizer is general at 200 degree or so,
Under air atmosphere, heating-up temperature higher, can there is a small amount of decomposition in the active component in slurry, while producing more being unfavorable for
The acidic site of reaction.Atomizing freeze drying is the combination of spray drying and freeze-drying, can make slurry rapid freeze-drying, and dry
Material afterwards is in granular form, and good fluidity, grain diameter is adjustable.
In the preparation method of catalyst of the present invention, step 1. in preroast and step 3. in calcination atmosphere be indifferent gas
The mixed gas that body is constituted with optional oxygen, the inert gas is at least one in nitrogen, helium, argon gas, preferably
In nitrogen, wherein step mixed gas 1., the volume fraction of oxygen is 0-60%, preferably 5-20%, step gaseous mixture 3.
In body, the volume fraction of oxygen is 0-60%, preferably 1-10%.
In the preparation method of catalyst of the present invention, step 2. middle binding agent consumption for catalyst powder weight 1-
5wt%, described binding agent is at least one in glycerine, polyvinyl alcohol, Ludox；The consumption of pore creating material is catalyst powder
The 1-5wt% of quality, described pore creating material is at least one in gum arabic powder, hydroxypropyl cellulose, wood fibre.
In the preparation method of catalyst of the present invention, step 2. obtained catalyst precursor be shaped as it is spherical, cylindrical, three
One or more of clover shape and hollow cylinder, preferably external diameter 3-5mm, wall thickness 1-2mm, the hollow cylinder of 3-5mm high,
More preferably external diameter 5mm, wall thickness 1.5mm, the hollow cylinder of 5mm high, thus obtained catalyst have preferably machinery strong
Degree and less bed pressure drop, are conducive to the raising in catalyst activity and life-span.
Catalyst of the invention is used to be catalyzed unsaturated olefin selective oxidation for unsaturated aldehyde or unsaturated acids, it is described not
Saturation of olefins is preferably propylene or isobutene, more preferably isobutene.
The beneficial effects of the present invention are：By catalyst obtained in the method for the present invention, with excellent heat transfer property,
Under relatively low hot(test)-spot temperature, excellent activity can be shown.It is applied to be catalyzed unsaturated olefin using catalyst of the present invention
Selective oxidation is unsaturated aldehyde or unsaturated acids, is particularly used for the reaction that catalyzing iso-butane alkene oxidation prepares MAL
When, under 400 DEG C or so of hot(test)-spot temperature, isobutene conversion can reach 99.5%, while MAL selectively may be used
To reach 84%.
Brief description of the drawings
Fig. 1 is the NH of embodiment and comparative example catalyst3The result that-TPD is characterized.
Specific embodiment
Catalyst provided by the present invention and preparation method thereof, but the present invention are further described by the following examples
Therefore it is not any way limited.
With Isosorbide-5-Nitrae-dioxane as internal standard compound during chromatography, the gas phase color of Japanese Shimadzu Corporation GC-2014C models is used
Spectrometer is analyzed.
Feed stock conversion and target product MAL in course of reaction, the selectivity of methacrylic acid calculating such as
Under：
The test of catalyst parameters and sign：
The thermal conductivity of heat transfer medium is tested using U.S.'s Anter FL4010 laser heat conducting instruments；Catalyst acid property table
Levy (NH3- TPD) tested using U.S. Kang Ta companies CHEMBET-3000TPD/TPR chemisorbeds desorption instrument.
Embodiment 1
The preparation of heat transfer medium
1) aluminium powder by 120g particle diameters for 400-800 μm is placed in ball grinder with the Ludox that mass concentration is 10wt%,
Powder submerges in Ludox completely, and ball-milling medium is the zirconia ball of particle diameter 2mm,
2) ball grinder is sealed, rolling ball milling 10h obtains slurry；
3) slurry is placed in baking oven, 140 DEG C of heat drying 2h obtain powder；
4) powder is placed in 1300 DEG C of roasting 3h in Muffle furnace, heating rate is 5 DEG C/min, obtains coated with silica
Aluminium powder, coating layer thickness is 3-8 μm.
The preparation of catalyst
1. under the conditions of 50 DEG C, by 400g ammonium heptamolybdates ((NH4)6Mo7O24.4H2O, molecular weight 1235.86), the inclined vanadium of 20g
Sour ammonium (NH4VO3, molecular weight 116.98) input 500m1 deionized waters in, obtain solution A after being completely dissolved.By 300g bismuth nitrates
(Bi(NO3)3·5H2O, molecular weight 485.1), 100g cobalt nitrates (Co (NO3)2·6H2O, molecular weight 291.05), 280g ferric nitrates
(Fe(NO3)39H2O molecular weight 404.02), 20g cesium carbonates (Cs2CO3, molecular weight 325.82), 20g copper nitrates (Cu
(NO3)2·3H2O, molecular weight 241.60) put into 425g dust technologies (15wt%) aqueous solution, obtain solution after being completely dissolved
B.It is 65 DEG C to keep solution temperature, and B is added into A in stirring, then adjusts pH=3 with ammoniacal liquor.Curing 5h is stirred at 65 DEG C, is obtained
To slurry.Slurry is placed in 4h in atomizing freeze drying machine, -60 DEG C of condenser temperature, atomisation pressure 4bar, vacuum pressure 10kpa,
Conditioning instrumentation parameter, control diameter of particle is at 30-300 μm.Powder is placed in Muffle furnace preroast 3h at 440 DEG C, was calcined
The gaseous mixture of oxygen and nitrogen composition is passed through in journey, oxygen purity is 15%.
2. by the catalyst powder (about 200g) after preroast and 10g wood fibres, 10g glycerine, 100g water, 100g heat transfers
Medium mixes, and extrusion obtains the hollow cylinder catalyst precursor of external diameter 5mm, wall thickness 1.5mm, 5mm high,
3. finally by catalyst precursor, calcination activation obtains catalyst in 3 hours in 500 DEG C, and oxygen is passed through in roasting process
The gaseous mixture of gas and nitrogen composition, oxygen purity is 10% in gaseous mixture.
Catalyst to being molded carries out NH3- TPD is characterized, and characterization result is as shown in Figure 1.
The oxidation reaction of isobutene
By Catalyst packing obtained above in the middle of fused salt device reaction pipe, reaction tube remainder is filled out by inert filler
Fill.Isobutylene oxidation condition is：Salt temperature is set as 350 DEG C, pressure 0.08MPa, the total air speed of reaction raw materials gaseous mixture
900h-1, water is 3 with isobutene molar ratio：1；Oxygen is 2 with isobutene mol ratio：1, nitrogen does make-up gas.Gained is produced
Thing carries out gas chromatographic analysis, hot(test)-spot temperature, isobutene conversion, MAL (acid) selection in catalyst activity evaluation
Property is as shown in table 1.
Embodiment 2
The preparation of heat transfer medium
1) aluminium powder by 40g particle diameters for 60-300 μm is placed in ball grinder with the Ludox that concentration is 50wt%, and powder is complete
Submerge in Ludox entirely, ball-milling medium is the zirconia ball of particle diameter 2mm,
2) ball grinder is sealed, rolling ball milling 2h obtains slurry；
3) slurry is placed in baking oven, 120 DEG C of heat drying 8h obtain powder；
4) powder is placed in 1300 DEG C of roasting 3h in Muffle furnace, heating rate is 5 DEG C/min, obtains coated with silica
Aluminium powder, coated with silica thickness degree is 5-10 μm.
The preparation of catalyst
According to embodiment 1, by step, 1. freeze-drying mode is changed to vacuum freeze drying, the freeze-drying 8h at -30 DEG C,
Step 1. powder preroast when mixed gas in, the volume fraction of oxygen is adjusted to 10%, step 3. catalyst precursor roasting
When, the volume fraction of oxygen is adjusted to 1% in mixed gas, and the consumption of step 2. middle heat transfer medium is changed to 50g.Remaining step is pressed
The method of embodiment 1 is prepared catalyst.
The oxidation reaction of isobutene
Catalyst activity evaluation, hot(test)-spot temperature, isobutene conversion, MAL are carried out with the method for embodiment 1
(acid) selectivity is as shown in table 1.Catalyst to being molded carries out NH3- TPD is characterized, and characterization result is as shown in Figure 1.
Embodiment 3
The preparation of heat transfer medium
1) iron-carbon alloy (carbon steel) by 120g particle diameters for 500-900 μm is placed in ball milling with the Ludox that concentration is 5wt%
In tank, powder submerges in Ludox completely, and ball-milling medium is the zirconia ball of particle diameter 2mm,
2) ball grinder is sealed, rolling ball milling 20h obtains slurry；
3) slurry is placed in baking oven, 110 DEG C of heat drying 10h obtain powder；
4) powder is placed in 1000 DEG C of roasting 4h in Muffle furnace, heating rate is 3 DEG C/min, obtains coated with silica
Aluminium powder, coated with silica thickness degree is 1-4 μm.
The preparation of catalyst
According to embodiment 1, by step 1. by powder preroast when mixed gas in, the volume fraction of oxygen is adjusted to
20%, step 3. catalyst precursor be calcined when, the volume fraction of oxygen is adjusted to 5% in mixed gas, and 2. step is conducted heat
The consumption of medium is changed to 140g.Remaining step is prepared catalyst as described in Example 1.
The oxidation reaction of isobutene
Catalyst activity evaluation, hot(test)-spot temperature, isobutene conversion, MAL are carried out with the method for embodiment 1
(acid) selectivity is as shown in table 1.Catalyst to being molded carries out NH3- TPD is characterized, and characterization result is as shown in Figure 1.
Comparative example 1
Aluminium powder in embodiment 1 is changed into silicon dioxide powder, other experimental implementation parameter constants.
Catalyst activity evaluation, hot(test)-spot temperature, isobutene conversion, MAL are carried out with the method for embodiment 1
(acid) selectivity is as shown in table 1.Catalyst to being molded carries out NH3- TPD is characterized, and characterization result is as shown in Figure 1.
Comparative example 2
The drying mode of slurry in embodiment 1 is changed into centrifugal spray drying, 220 DEG C of drying machine inlet temperature is controlled,
The calcination atmosphere of 100 DEG C of outlet, powder and preformed catalyst is changed to air atmosphere, other experimental implementation parameter constants.
Catalyst activity evaluation, hot(test)-spot temperature, isobutene conversion, MAL are carried out with the method for embodiment 1
(acid) selectivity is as shown in table 1.Catalyst to being molded carries out NH3- TPD is characterized, and characterization result is as shown in Figure 1.
Table 1
Claims (11)
1. a kind of catalyst, it is characterised in that the catalyst has below formula：
Mo12BiaFebCocCudCseVfOy/M
Wherein, a, b, c, d, e, f represent the atomic ratio of corresponding element respectively, a=0.5~5, b=0.5~5, c=0.5~5,
D=0.02~1, e=0.2~1, f=0~3, y is the atomic ratio for meeting oxygen required for each element chemical valence；M represents cladding
Type heat transfer medium, the cladded type heat transfer medium is coated with silica metal powder and/or coated with silica alloyed powder.
2. catalyst according to claim 1, it is characterised in that in the cladded type heat transfer medium, silica accounts for biography
The 0.1-1wt% of thermal medium gross weight；Coating layer thickness of the silica on metal powder or alloyed powder surface is 0.1-50 μm, preferably
1-10μm。
3. catalyst as claimed in claim 1 or 2, it is characterised in that the cladded type heat transfer medium accounts for overall catalyst weight
5-50wt%, preferably 10-30wt%；The particle diameter of heat transfer medium is 50-1000 μm, is preferably 200-800 μm.
4. catalyst as claimed in claim 1 or 2, it is characterised in that when in described heat transfer medium by coated with silica
Be metal powder when, metallic element is selected from least one in beryllium, aluminium, magnesium, nickel, iron, titanium, preferably aluminium；When by silica bag
Cover be alloyed powder when, the metallic element of alloy is selected from least one in beryllium, aluminium, magnesium, nickel, iron, titanium, the nonmetallic unit of alloy
Selected from least one in carbon, boron, silicon, phosphorus, in alloy, nonmetalloid accounts for the 0.01%-5wt% of weight alloy to element.
5. the catalyst as described in claim any one of 1-4, it is characterised in that the preparation method of heat transfer medium includes following step
Suddenly：
1) metal powder or alloyed powder are placed in ball grinder with the Ludox that concentration is 5-50wt%, preferably 10-15wt%；
2) ball grinder is sealed, rolling ball milling obtains slurry；
3) by step 2) slurry drying that obtains, obtain powder；
4) powder is placed in Muffle furnace and is calcined, obtain heat transfer medium.
6. a kind of method for preparing the catalyst described in claim any one of 1-5, it is characterised in that methods described includes following
Step：
1. by the atomic ratio of each element composition, the water solubility for containing Mo, Bi, Fe, Co, Cu, Cs, V element is dissolved with water or diluted acid
Or acid-soluble compound, pH=0.5~7, preferably pH=2~4 are adjusted with ammoniacal liquor after being well mixed, it is followed by aging to obtain containing work
The slurry of property component, by preroast after slurry freeze-drying, obtains catalyst powder,
2. catalyst powder is obtained into catalyst precursor with including heat transfer medium and pore creating material, binding agent mixed-forming,
3. catalyst precursor roasting is obtained into catalyst.
7. method as claimed in claim 6, it is characterised in that the step 1. freeze-drying, dries, true selected from air freezing
Vacuum freecing-dry or atomizing freeze drying, preferably atomizing freeze drying；The temperature of freeze-drying is -60~0 DEG C, freeze-drying
Time is 4-16h.
8. method as claimed in claim 6, it is characterised in that step 1. in preroast and step 3. in calcination atmosphere be
The mixed gas that inert gas is constituted with optional oxygen, the inert gas is at least one in nitrogen, helium, argon gas,
Preferably nitrogen, wherein in step mixed gas 1., the volume fraction of oxygen is 0-60%, preferably 5-20%, and step is 3.
In mixed gas, the volume fraction of oxygen is 0-60%, preferably 1-10%.
9. preparation method according to claim 6, it is characterised in that the consumption of step 2. middle binding agent is catalyst powder
The 1-5wt% of quality, described binding agent is at least one in glycerine, polyvinyl alcohol, Ludox；The consumption of pore creating material is to urge
The 1-5wt% of agent powder quality, described pore creating material in gum arabic powder, hydroxypropyl cellulose, wood fibre extremely
Few one kind.
10. method according to claim 6, it is characterised in that the 2. described catalyst precursor of step be shaped as it is spherical,
One or more of cylinder, cloverleaf pattern and hollow cylinder, preferably external diameter 3-5mm, wall thickness 1-2mm, the sky of 3-5mm high
Heart cylinder, more preferably external diameter 5mm, wall thickness 1.5mm, the hollow cylinder of 5mm high.
11. as described in claim any one of 1-5 catalyst or the catalyst according to obtained in claim 6-10 any one methods
Purposes, for being catalyzed unsaturated olefin selective oxidation for unsaturated aldehyde or unsaturated acids, the unsaturated olefin is preferably
Propylene or isobutene, more preferably isobutene.
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| CN112547082A (en) * | 2019-09-25 | 2021-03-26 | 中国石油化工股份有限公司 | Catalyst for preparing acrylic acid by acrolein oxidation and preparation method and application thereof |
| CN114425326A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst suitable for producing acrolein and preparation method and application thereof |
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| CN107915758A (en) * | 2017-11-15 | 2018-04-17 | 万华化学集团股份有限公司 | Phosphoramidite ligand, catalyst and the method for preparing 4 acetoxyl group butyraldehyde |
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| CN112547082A (en) * | 2019-09-25 | 2021-03-26 | 中国石油化工股份有限公司 | Catalyst for preparing acrylic acid by acrolein oxidation and preparation method and application thereof |
| CN112547082B (en) * | 2019-09-25 | 2023-08-29 | 中国石油化工股份有限公司 | Catalyst for preparing acrylic acid by acrolein oxidation and preparation method and application thereof |
| CN114425326A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst suitable for producing acrolein and preparation method and application thereof |
| CN114425326B (en) * | 2020-10-15 | 2024-02-02 | 中国石油化工股份有限公司 | Catalyst suitable for producing acrolein and preparation method and application thereof |
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