CN106040314B - The preparation and application of a kind of coated catalysts using ionic liquid as binder - Google Patents
The preparation and application of a kind of coated catalysts using ionic liquid as binder Download PDFInfo
- Publication number
- CN106040314B CN106040314B CN201610413058.8A CN201610413058A CN106040314B CN 106040314 B CN106040314 B CN 106040314B CN 201610413058 A CN201610413058 A CN 201610413058A CN 106040314 B CN106040314 B CN 106040314B
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- Prior art keywords
- ionic liquid
- coated catalysts
- catalyst
- preparation
- binder
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 179
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000011230 binding agent Substances 0.000 title claims description 19
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 53
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000003647 oxidation Effects 0.000 claims abstract description 29
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 26
- 239000007921 spray Substances 0.000 claims abstract description 23
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000011148 porous material Substances 0.000 claims description 19
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 18
- 238000005507 spraying Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 13
- 238000001694 spray drying Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 5
- -1 pelelith Chemical compound 0.000 claims description 5
- 239000004575 stone Substances 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000011268 mixed slurry Substances 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 4
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- 229910003827 NRaRb Inorganic materials 0.000 claims 1
- 150000001450 anions Chemical class 0.000 claims 1
- 229910052712 strontium Inorganic materials 0.000 claims 1
- 229910052718 tin Inorganic materials 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 32
- 238000000576 coating method Methods 0.000 abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 238000009826 distribution Methods 0.000 abstract description 5
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 abstract description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052797 bismuth Inorganic materials 0.000 abstract description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 2
- 239000011733 molybdenum Substances 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 239000002002 slurry Substances 0.000 description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 239000000126 substance Substances 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- 230000002194 synthesizing effect Effects 0.000 description 15
- 230000001590 oxidative effect Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- ACWQBUSCFPJUPN-UHFFFAOYSA-N 2-methylbut-2-enal Chemical compound CC=C(C)C=O ACWQBUSCFPJUPN-UHFFFAOYSA-N 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- 206010013786 Dry skin Diseases 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 230000000750 progressive effect Effects 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000006004 Quartz sand Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- HCGMDEACZUKNDY-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCCCN1CN(C)C=C1 HCGMDEACZUKNDY-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000011964 heteropoly acid Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- 229910002480 Cu-O Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical class [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 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 2
- 230000006870 function Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- OSFGNZOUZOPXBL-UHFFFAOYSA-N nitric acid;trihydrate Chemical class O.O.O.O[N+]([O-])=O OSFGNZOUZOPXBL-UHFFFAOYSA-N 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- GTCDARUMAMVCRO-UHFFFAOYSA-M tetraethylazanium;acetate Chemical class CC([O-])=O.CC[N+](CC)(CC)CC GTCDARUMAMVCRO-UHFFFAOYSA-M 0.000 description 2
- PXJUBOLFJDSAQQ-UHFFFAOYSA-M tetrapropylazanium;acetate Chemical class CC([O-])=O.CCC[N+](CCC)(CCC)CCC PXJUBOLFJDSAQQ-UHFFFAOYSA-M 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- ZXLOSLWIGFGPIU-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical compound CC(O)=O.CCN1CN(C)C=C1 ZXLOSLWIGFGPIU-UHFFFAOYSA-N 0.000 description 1
- WGVGZVWOOMIJRK-UHFFFAOYSA-N 1-hexyl-3-methyl-2h-imidazole Chemical compound CCCCCCN1CN(C)C=C1 WGVGZVWOOMIJRK-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910020647 Co-O Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910020704 Co—O Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229940000488 arsenic acid Drugs 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
- 238000007664 blowing Methods 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 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
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical class O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical class [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical class O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- OOAWCECZEHPMBX-UHFFFAOYSA-N oxygen(2-);uranium(4+) Chemical compound [O-2].[O-2].[U+4] OOAWCECZEHPMBX-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical class [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- FCTBKIHDJGHPPO-UHFFFAOYSA-N uranium dioxide Inorganic materials O=[U]=O FCTBKIHDJGHPPO-UHFFFAOYSA-N 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- 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
- B01J23/8876—Arsenic, antimony or bismuth
-
- 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
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
-
- 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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8898—Manganese, technetium or rhenium containing also molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The present invention relates to a kind of method and its application being used to prepare coated catalysts.The method of the prepares coating catalyst is to be coated to the catalyst powder for containing active component on inert carrier under the action of ionic liquid, the outer layer active component of obtained coated catalysts contains the oxides such as molybdenum, bismuth, and internal layer is the inert carriers such as aluminium oxide, silica.When catalyst preparation, can by catalyst powder, ionic liquid, (or respectively) dispersion in ethanol, and sprays on inertia ball type carrier (simultaneously) together, obtain coated catalysts.The catalyst forms the hole of specific distribution after the processing such as drying, roasting, with higher mechanical strength, and when propylene oxidation prepares methacrylaldehyde, (methyl) acrolein oxidation prepares (methyl) acrylic acid and isobutylene oxidation prepares methacrolein with excellent reactivity worth.
Description
Technical field
The present invention relates to a kind of using ionic liquid as the preparation of the coated catalysts of binder and its application, belongs to catalyst
Preparation and application field.
Background technology
The selective oxidation of alkene prepares α, β unsaturated aldehyde and unsaturated acids is important chemical process in industrial production,
In typical reaction process have propylene oxidative synthesis methacrylaldehyde, acrolein oxidation acrylic acid synthesizing, isobutylene oxidation synthesizing methyl
Methacrylaldehyde and methacrolein oxidative synthesis methacrylic acid.Currently, such catalyst for using of reaction is mainly that molybdenum, bismuth system are more
Component composite metal catalyst and heteropolyacid catalyst, wherein multicomponent O composite metallic oxide catalyst have propylene oxidative synthesis
The Mo-Bi-Fe-Co-O catalyst of methacrylaldehyde, the Mo-V-Cu-O catalyst of acrolein oxidation acrylic acid synthesizing and isobutylene oxidation
The Mo-Bi-Cs-Fe-O catalyst of synthesizing methyl methacrylaldehyde, heteropolyacid catalyst are methacrolein oxidative synthesis metering system
The Mo-P-V-Cu-O catalyst of acid.At present since the specific surface area of such catalyst is more relatively low, difficult forming and active component are sharp
It is low with rate, cause its industry amplification more difficult.
Patent document CN104649875A, CN103769148A, CN104549353A are by using extrusion or compression molding
Mode improve the mechanical strength of catalyst, but catalyst activity component utilization rate is relatively low；Patent document CN101088608A is carried
Go out and be combined with three kinds of co-precipitation, ultrasonic wave and microwave methods, is prepared for the preferable molybdenum-bismuth-antimony composite oxides of dispersion effect
Catalyst, but the active component utilization rate of molding rear catalyst and mechanical strength are all relatively low.
Patent document CN101980781A proposes the organic matter that easy burning-off is added in the catalyst, by being removed in roasting
These organic matters achieve the purpose that pore-creating, to improve the Kong Rong of catalyst.But there are short life, work for the catalyst of the disclosure report
The disadvantages such as property component utilization rate is low.
Patent document CN104437476A proposes the method that spray-on process prepares catalyst, will be contained using sprayer active
The solution even application of component is reached in inert carrier surface to improve the dispersion degree and utilization ratio of catalyst activity component
To the effect for improving catalyst reaction performance, but the active component utilization rate of catalyst is relatively low.
Patent document CN104525242A proposes the preparation method of molecular sieve integral type catalyst, utilizes painting method
It is prepared for molecular sieve coating catalyst, improves the utilization rate of catalyst, but catalyst easily peels off, bad mechanical strength；Patent text
It offers CN0185995.8 propositions adhesive and coated catalysts, but the bonding operation is made on a inert carrier by catalyst coated
It is complicated, it is desirable that it is high, and catalytic mechanical intensity obtained is relatively low.
Patent document CN104801351A utilizes spraying method prepares coating catalyst, and macromolecule is added in preparation process
Organic compound improves the mechanical strength of catalyst and the utilization rate of active component as binder, but its high score for using
Sub- organic compound molecule amount is wide, and carburizing temperature range is big, causes the pore-creating of coated catalysts selectivity difficult, and in roasting process
In can be remained, the performance of catalyst is impacted；In addition, the macromolecular organic compound is easily anti-with catalyst pulp
It answers, it is more demanding to spraying equipment, it is complicated for operation.
Compared with macromolecular organic compound, ionic liquid has the advantages that structure size and chemical property are adjustable,
During using it as binder prepares coating catalyst, the ionic liquid of different structure size is selected, it will in roasting process
It removes and selectively obtains required aperture and pore-size distribution completely；In addition, according to the change of different catalysts slurry
Learning property selects suitable ionic liquid to be mixed, and is sprayed using single fluid, simplifies spraying operation step.Therefore, with ion
Liquid is a kind of preparation method of great foreground as binder prepares coating catalyst.
Invention content
An object of the present invention is selective acquisition aperture and pore-size distribution, proposes that a kind of with ionic liquid is to bond
The preparation method of the coated catalysts of agent.This method selects the ionic liquid of different structure as binder, using spraying legal system
Standby coated catalysts, the ionic liquid being entrained in outer layer active component is removed after certain temperature roasts, obtains different holes
Diameter and pore-size distribution, selectively adjust the pore structure of catalyst, and active component utilization rate and the machinery for improving catalyst are strong
Degree.
The second object of the present invention is to simplify the preparation process of coated catalysts, propose a kind of by catalyst powder and ion
Liquid solution mixes, and is sprayed using single fluid operating method, and at low cost, favorable reproducibility coated catalysts are obtained.
The third object of the present invention is to provide the purposes of above-mentioned coated catalysts, which is used for propylene oxidative synthesis
With excellent when methacrylaldehyde, isobutylene oxidation synthesizing methyl methacrylaldehyde and (methyl) acrolein oxidation synthesis (methyl) acrylic acid
Conversion ratio and selectivity.
To achieve the above objectives, the present invention adopts the following technical scheme that：
A kind of preparation method of coated catalysts, includes the following steps：
(a) under certain condition, required dissolving metal salts are mixed and added into precipitating reagent, obtain catalyst pulp, and
Aging is spare under certain condition.
(b) suspension obtained by drying process (a) under certain condition, obtains required catalyst powder.
(c) in ethanol by the dispersion of a certain amount of ionic liquid, ionic liquid solution is obtained.
(d) by the catalyst powder that process (b) obtains be added to process (c) obtained ionic liquid solution in, obtain
To the mixed slurry of catalyst and ionic liquid.
(e) mixed slurry obtained in process (d) is sprayed on sphere inert carrier, obtains coated catalysts.
(f) coated catalysts will be obtained in process (e) and are placed under certain temperature to be dried.
(g) catalyst after the drying obtained in process (f) is placed in tube furnace under certain condition and is roasted.
The compound of each element used in process (a) need to be dissolved in water, remaining can use its nitric acid without specifically limited
Salt, chloride, acetate etc., the preferably nitrate of metallic element.
The precipitating reagent that is used in process (a) is chosen but is not limited to ammonium molybdate, ammonium metavanadate, potassium hydroxide, sodium hydroxide etc.,
According to the precipitating reagent that different selecting responses is optimal.
Pneumatic spray drying, centrifugal spray drying, or even evaporation may be used in the drying means used in process (b)
It is dry, filter dry, the preferred pneumatic spray drying method of the present invention, inlet temperature is 120~240 DEG C when spray drying,
Outlet temperature is 70~160 DEG C.
At 0.1~20 μm, preferred scope is 2~15 μ for the particle size range control of dry gained catalyst powder in process (b)
m。
The mass ratio of catalyst powder and process (c) ionic liquid used in process (d) is 200~10:1, preferably
100~50:1, the ionic liquid of too low ratio can make the stickiness of catalyst powder reduce, and be unfavorable for the knot of catalyst and carrier
It closes, excessively a high proportion of ionic liquid can so that the coating in roasting process easily bursts apart the cost caved in, and can increase catalyst.
In order to make the catalyst powder in process (d) preferably disperse, the quality of catalyst powder and ethyl alcohol in process (c)
Than being 4~0.3:1, preferably 2~0.5:1, and water content≤10wt% in ethyl alcohol, preferably water content≤5wt% should be controlled.
Spray gun used in process (e) is import anti-corrosion spray gun, and spraying operation uses single fluid spray pattern.
Spraying equipment used in process (e) is the small-sized seed-coating machine of test-type, is heated using blowing hot wind mode, heating temperature
Degree is 30~90 DEG C, and preferably 50~80 DEG C, excessively high temperature can cause coated catalysts to burst apart and uneven, too low temperature
Spraying rate is reduced, rate of catalyst loss increases, coated catalysts lack of homogeneity.
Forced air drying, vacuum drying and microwave drying can be selected in the drying mode used in process (f), and preferably air blast is dry
Dry and vacuum drying；Drying temperature is 40~110 DEG C, and preferably 60~90 DEG C, drying time is 2~18 hours, and preferably 4~15 is small
When.
The catalyst after drying is roasted in process (h) by the way of baking inphases：First segment be inert atmosphere under 200~
550 DEG C roast 1~8 hour, preferably 300~450 DEG C of calcination temperature, roasting time preferably 2~4 hours；Second segment is oxidisability
It is roasted 2~10 hours for 240~550 DEG C under atmosphere, preferably 300~500 DEG C of calcination temperature, roasting time preferably 3~8 hours.
Sphere inert carrier of the present invention includes mainly aluminium oxide, pelelith, molecular sieve, red pottery stone etc., preferably oxygen
Change aluminium and red pottery stone, Carrier diameters are 1~6mm, and water absorption rate is 10~40wt%.
In the present invention, the outer layer active component of obtained coated catalysts and the mass ratio of ball type carrier are 2~0.1:
1, preferably 1.3~0.2:1.
Heretofore described inert gas is optional but is not limited to nitrogen, argon gas, helium, preferably nitrogen；The oxidation
Property atmosphere refer to such as oxygen or pure oxygen of the gas containing oxidizing substance, preferably oxygen concentration be 10~30% gas
Mixture, such as air.
Drying process of the present invention is primarily to remove the ethyl alcohol in coated catalysts；First segment roasting process
Main function is the interaction between fortifying catalytic agent powder and ionic liquid, makes the ionic liquid contacted with catalyst powder
It decomposes, forms certain pore structure, but do not destroy the structure of catalyst；The main function of second segment roasting process is oxidation point
Catalyst is solved, required active sites are obtained.
Coated catalysts obtained by the present invention can be applied to propylene oxidative synthesis methacrylaldehyde, acrolein oxidation synthesis propylene
The reaction system of acid, isobutylene oxidation synthesizing methyl methacrylaldehyde and methacrolein oxidative synthesis methacrylic acid.Raw material propylene,
After methacrylaldehyde, isobutene or methacrolein and air or admixture of gas containing a certain amount of oxygen are preheated, it is passed through and is equipped with
Reaction synthesis purpose product is carried out in the fixed bed reactors of catalyst.Admixture of gas used containing a certain amount of oxygen,
Oxygen content is 10~50%, remaining component can be the mixture of one or more kinds of inert gases such as nitrogen, helium, argon gas.
Coated catalysts of the present invention are for propylene oxidative synthesis methacrylaldehyde, acrolein oxidation acrylic acid synthesizing, different
The reaction condition of butylene oxidation synthesizing methyl methacrylaldehyde and methacrolein oxidative synthesis methacrylic acid is shown in example.
Specific implementation mode
The present invention is illustrated with embodiment below, but the scope of the present invention should not be limited by the examples.
Catalyst load percentage is defined as follows：
W (catalyst) %=[(quality-carrier qualities of coated catalysts)/carrier quality] × 100%
Embodiment 1
(a) preparation of propylene oxidative synthesis methacrylaldehyde catalyst
1000mL deionized waters are measured, 1000.0g ammonium molybdates are added, 70 DEG C of stirred in water bath dissolvings is placed in, waits for it completely
2.9g potassium nitrate and 5.5g cesium nitrates are added after dissolving, adds the Ludox of a concentration of 40wt% of 573.9g, obtains material A；
150mL deionized waters are measured, nine water ferric nitrates of 396.9g are added, are placed in 70 DEG C of stirred in water bath dissolvings, after it is completely dissolved,
It is separately added into five water bismuth nitrates of 229.0g again, 480.8g cobalt nitrate hexahydrates, six water nickel nitrates of 452.1g, 150.5g are a concentration of
Manganese nitrate aqueous solution, 19.6g nitrate trihydrates lanthanum and the 41.7g antimony oxides of 50wt%, stirs to get material B；By material B
It is added in material A under fast stirring, forms catalyst pulp, and stir aging 2 hours at 65 DEG C, obtain required catalysis
Agent slurry.
A certain amount of above-mentioned catalyst suspension is weighed, which is placed on pneumatic spray drying device spray and is done
Dry, compressed air flow velocity is 10L/min, and the inlet temperature of spray dryer is 180~200 DEG C, and outlet temperature is 123~128
DEG C, charging pump speed is 450~500mL/h, obtains required catalyst powder, and average grain diameter is 8.0 μm.
It takes 3.0g 1- butyl -3- methylimidazole acetate to be dissolved in the ethyl alcohol that 300g water contents are 5wt% and obtains slurry
(being denoted as slurry A) takes 200g catalyst powders to be dispersed in slurry A, obtains slurry B, and obtained slurry B is sprayed to seed-coating machine
On the alumina balls of a diameter of 2~3mm of 100g of middle progressive rolling movement, in spraying process, the set temperature of seed-coating machine is 70 DEG C, whole
A intermittent spray process takes 45min altogether, obtains coated catalysts.
The coated catalysts of gained are placed in air dry oven 80 DEG C of dryings 5 hours.Again by the catalyst after drying into
Row roasting, stops 3 hours under 350 DEG C of nitrogen atmospheres, is stopped 4 hours under 500 DEG C of air atmospheres, finally obtains coating catalysis
Agent.
Coated catalysts after above-mentioned roasting are subjected to Analysis of Physical：Its catalyst load percentage is 28%, abrasion
Index is 2.1%；The hole contained hole appearance that aperture is 20~1000nm in outer layer active component accounts for the 76% of total pore volume, aperture 50
Kong Rong shared by the hole of~500nm accounts for the 42% of total pore volume.
(b) reaction of propylene oxidative synthesis methacrylaldehyde
The obtained coated catalysts of 1.2g are loaded in the fixed bed reactors that internal diameter is 12mm, catalyst is equal up and down
The quartz sand of the grain sizes such as filling, with air:Propylene：Vapor=73:10:17 (molar ratios) are raw material, air speed 1200h-1, pressure
It is reaction condition that power (absolute pressure), which is 0.05MPa, is reacted 4 hours at 375 DEG C.
Propylene conversion is defined as follows：
X (propylene) %=[1- (amount of the substance of the propylene of amount/supply of the substance of unreacted propylene)] × 100%
Methacrylaldehyde selectivity of product is defined as follows：
S (methacrylaldehyde) %=[amounts of the substance of the methacrylaldehyde of the generation/(amount-unreacted third of the substance of the propylene of supply
The amount of the substance of alkene)] × 100%
Through gas-chromatography on-line analysis and calculate, experimental result be propylene conversion ratio 95.6%, the selectivity of methacrylaldehyde
87.2%.
Embodiment 2
In addition to the 1- butyl -3- methylimidazole acetate in embodiment 1 is changed to 1- hexyl -3- methylimidazole caproates,
Other are prepared as described in Example 1, obtain coated catalysts.The load percentage of its catalyst is 31%, and abrasion refers to
Number test result is 3.4%；The hole contained hole appearance that aperture is 20~1000nm in outer layer active component accounts for the 78% of total pore volume, hole
Diameter is that the Kong Rong shared by the hole of 50~500nm accounts for the 45% of total pore volume.
It is small to react 4 at 375 DEG C for the reaction for carrying out propylene oxidative synthesis methacrylaldehyde in the same manner as shown in Example 1
When, it through gas-chromatography on-line analysis and calculates, experimental result is the conversion ratio 91.1% of propylene, the selectivity of methacrylaldehyde
89.8%.
Embodiment 3
(a) preparation of acrolein oxidation acrylic acid synthesizing catalyst
500mL deionized waters are measured, tetra- water ammonium heptamolybdates of 500.0g are added, 70 DEG C of stirred in water bath dissolvings is placed in, obtains
Solution A；250mL deionized waters are measured, 129.0g ammonium metavanadates are added, 70 DEG C of stirred in water bath dissolvings is placed in, obtains solution B；
100mL deionized waters are measured, 52.1g antimony oxides are added, 70 DEG C of stirred in water bath dissolvings are placed in, after it is completely dissolved
171.0g nitrate trihydrates copper, 60.0g strontium nitrates and 63.5g ammonium tungstates, stirring and dissolving is added and obtains solution C；Measure 20mL go from
Sub- water is added 9.5g Strong oxdiative potassium, is placed in stirring and dissolving under room temperature, it is a concentration of to be added to 322.0g after it is completely dissolved
In the Ludox of 40wt%, stirring at normal temperature obtains material D after 15 minutes；Material D is added in solution A, waits for that it is uniformly mixed
Solution B is added again afterwards, is uniformly mixed, solution C is added, stirring forms catalyst suspension.
A certain amount of above-mentioned catalyst suspension is weighed, which is placed on pneumatic spray drying device spray and is done
Dry, compressed air flow velocity is 10L/min, and the inlet temperature of spray dryer is 170~185 DEG C, and outlet temperature is 93~95 DEG C,
Charging pump speed is 500~550mL/h, obtains required catalyst powder, and average grain diameter is 10.0 μm.
It takes 3.6g 1- ethyl-3-methylimidazole acetate to be dissolved in the ethyl alcohol that 400g water contents are 5wt% and obtains slurry
(being denoted as slurry A) takes 300g catalyst powders to be dispersed in slurry A, obtains slurry B, and obtained slurry B is sprayed to seed-coating machine
On the red pottery stone bead of a diameter of 3~4mm of 100g of middle progressive rolling movement, in spraying process, the set temperature of seed-coating machine is 70 DEG C,
Entire intermittent spray process takes 35min altogether, obtains coated catalysts.
The coated catalysts of gained are placed in air dry oven 80 DEG C of dryings 5 hours.Again by the catalyst after drying into
Row roasting, stops 3 hours under 350 DEG C of nitrogen atmospheres, is stopped 6 hours under 430 DEG C of air atmospheres, finally obtains coating catalysis
Agent.
Coated catalysts after above-mentioned roasting are subjected to Analysis of Physical：Its catalyst load percentage is 38%, abrasion
Index is 2.1%；The hole contained hole appearance that aperture is 20~1000nm in outer layer active component accounts for the 74% of total pore volume, aperture 50
Kong Rong shared by the hole of~500nm accounts for the 39% of total pore volume.
(b) reaction of acrolein oxidation acrylic acid synthesizing
The obtained coated catalysts of 1.2g are loaded in the fixed bed reactors that internal diameter is 12mm, catalyst is equal up and down
The quartz sand of the grain sizes such as filling, with air:Methacrylaldehyde：Vapor=36:24:40 (molar ratios) are raw material, air speed 1200h-1,
It is reaction condition that pressure (absolute pressure), which is 0.02MPa, is reacted 4 hours at 280 DEG C.
Reaction product gas-chromatography on-line analysis.
Acrolein conversion rate is defined as follows：
X (methacrylaldehyde) %=[1- (amount of the substance of the methacrylaldehyde of amount/supply of the substance of unreacted methacrylaldehyde)] ×
100%
Acrylic acid product selectivity is defined as follows：
S (acrylic acid)=[amount of the substance of the acrylic acid of the generation/(amount-unreacted third of the substance of the methacrylaldehyde of supply
The amount of the substance of olefine aldehydr)] × 100%
Through gas-chromatography on-line analysis and calculate, experimental result be methacrylaldehyde conversion ratio 94.8%, the selection of acrylic acid
Property 98.5%.
Embodiment 4
O composite metallic oxide catalyst powder is prepared with reference to embodiment 3, then following steps prepares coating is used to be catalyzed
Agent：It takes 3.6g tetrapropyl ammonium acetates to be dissolved in the ethyl alcohol that 300g water contents are 5wt% and obtains slurry (being denoted as slurry A), take
300g catalyst powders are dispersed in slurry A, obtain slurry B, and obtained slurry B is sprayed to progressive rolling movement in seed-coating machine
On the red pottery stone bead of a diameter of 3~4mm of 150g, in spraying process, the set temperature of seed-coating machine is 60 DEG C, entire intermittent spray
Process takes 30min altogether, obtains coated catalysts.
The coated catalysts of gained are placed in air dry oven 80 DEG C of dryings 5 hours.Again by the catalyst after drying into
Row roasting, stops 3 hours under 350 DEG C of nitrogen atmospheres, is stopped 6 hours under 430 DEG C of air atmospheres, finally obtains coating catalysis
Agent.
Coated catalysts after above-mentioned roasting are subjected to Analysis of Physical：Its catalyst load percentage is 40%, abrasion
Index is 3.3%；The hole contained hole appearance that aperture is 20~1000nm in outer layer active component accounts for the 81% of total pore volume, aperture 50
Kong Rong shared by the hole of~500nm accounts for the 46% of total pore volume.
The reaction that acrolein oxidation acrylic acid synthesizing is carried out according to method same as Example 3, reacts 4 at 280 DEG C
Hour, it through gas-chromatography on-line analysis and calculates, experimental result is the conversion ratio 98.6% of methacrylaldehyde, the selectivity of acrylic acid
97.0%.
Embodiment 5
(a) preparation of isobutene gaseous oxidation synthesizing methyl methacrylaldehyde catalyst
3000mL deionized waters are measured, 270.0g ammonium molybdates are added, 50 DEG C of stirred in water bath dissolvings is placed in, obtains solution A；
292.5g cobalt nitrates, 4.5g potassium nitrate, 4.5g cesium nitrates, 45.0g are added into the aqueous solution of nitric acid of a concentration of 15wt% of 300mL
Ferric nitrate, 90.0g bismuth nitrates and 22.5g cerous nitrates, obtain solution B；Solution B is added dropwise to the solution A under 50 DEG C of stirrings
In, ammonium hydroxide is added dropwise after being added dropwise to complete, it is stirring aging 8 hours at 3.0,50 DEG C to adjust pH, obtains catalyst suspension.
A certain amount of above-mentioned catalyst suspension is weighed, which is placed on pneumatic spray drying device spray and is done
Dry, compressed air flow velocity is 8L/min, and the inlet temperature of spray dryer is 220~230 DEG C, and outlet temperature is 135~145
DEG C, charging pump speed is 450~500mL/h, and the average grain diameter for obtaining catalyst powder is 12 μm.
It takes 2.5g tetrapropyl ammonium acetates to be dissolved in the ethyl alcohol that 300g water contents are 5wt% and obtains slurry (being denoted as slurry A),
It takes 150g catalyst powders to be dispersed in slurry A, obtains slurry B, obtained slurry B is sprayed into progressive rolling movement in seed-coating machine
On the alumina balls of a diameter of 1~2mm of 100g, in spraying process, the set temperature of seed-coating machine is 60 DEG C, entire intermittent spray mistake
Journey takes 40min altogether, obtains coated catalysts.
The coated catalysts of gained are placed in air dry oven 70 DEG C of dryings 5 hours.Again by the catalyst after drying into
Row roasting, stops 3 hours under 350 DEG C of nitrogen atmospheres, is stopped 5 hours under 400 DEG C of air atmospheres.Finally obtain coating catalysis
Agent.
Coated catalysts after above-mentioned roasting are subjected to Analysis of Physical：Its catalyst load percentage is 35%, abrasion
Index is 2.6%；The hole contained hole appearance that aperture is 20~1000nm in outer layer active component accounts for the 82% of total pore volume, aperture 50
Kong Rong shared by the hole of~500nm accounts for the 49% of total pore volume.
(b) reaction of isobutylene oxidation synthesizing methyl methacrylaldehyde
The obtained coated catalysts of 0.6mL are loaded in the fixed bed reactors that internal diameter is 12mm, above and below catalyst
The quartz sand of the grain sizes such as filling, with air:Isobutene=25:1 (molar ratio) is raw material, air speed 9000h-1, pressure is (absolutely
Pressure) be 0.15MPa it is reaction condition, it is reacted 2 hours at 320 DEG C, 380 DEG C respectively.
Reaction product gas-chromatography on-line analysis.
The conversion ratio of isobutene is defined as follows：
X (isobutene) %=[1- (amount of the substance of the isobutene of amount/supply of the substance of unreacted isobutene)] ×
100%
The selectivity of methacrolein is defined as follows：
S (methacrolein) %=[amounts of the substance of the methacrolein of the generation/(amount-of the substance of the isobutene of supply
The amount of the substance of unreacted isobutene)] × 100%
It is respectively 67.6%, 89.8% that isobutene, which is measured, in the conversion ratio of 320 DEG C and 380 DEG C, the selection of methacrolein
Property is respectively 77.3%, 75.0%.Successive reaction is after 10 hours at 380 DEG C, and the conversion ratio for measuring isobutene is 88.1%, first
The selectivity of base methacrylaldehyde is 74.6%.
Embodiment 6
O composite metallic oxide catalyst powder is prepared with reference to embodiment 5, then following steps prepares coating is used to be catalyzed
Agent：It takes 2.5g tetraethyl ammonium acetates to be dissolved in the ethyl alcohol that 300g water contents are 15wt% and obtains slurry (being denoted as slurry A), take
150g catalyst powders are dispersed in slurry A, obtain slurry B, and obtained slurry B is sprayed to progressive rolling movement in seed-coating machine
On the alumina balls of a diameter of 1~2mm of 100g, in spraying process, the set temperature of seed-coating machine is 30 DEG C, entire intermittent spray mistake
Seed-coating machine fused glass inside is more serious in journey, takes 70min altogether, obtains coated catalysts.
The coated catalysts of gained are placed in air dry oven 70 DEG C of dryings 5 hours.Again by the catalyst after drying into
Row roasting, stops 3 hours under 350 DEG C of nitrogen atmospheres, is stopped 5 hours under 400 DEG C of air atmospheres.Finally obtain coating catalysis
Agent.
Coated catalysts after above-mentioned roasting are subjected to Analysis of Physical：Its catalyst load percentage is 16%, abrasion
Index is 7.6%；The hole contained hole appearance that aperture is 20~1000nm in outer layer active component accounts for the 76% of total pore volume, aperture 50
Kong Rong shared by the hole of~500nm accounts for the 33% of total pore volume.
The reaction that isobutylene oxidation synthesizing methyl methacrylaldehyde is carried out according to method same as Example 5,320 DEG C, 380
It is reacted 2 hours at DEG C, the conversion ratio for measuring isobutene is respectively 41.3%, 65.8%, and the selectivity of methacrolein is respectively
69.8%, 74.0%.Successive reaction is after 10 hours at 380 DEG C, and the conversion ratio for measuring isobutene is 61.1%, methacrolein
Selectivity be 71.6%.
Embodiment 7
(a) preparation of methacrolein oxidative synthesis metering system acid catalyst
Measure 4000mL deionized waters, be added 490.5g molybdenum trioxides, 18.2g vanadic anhydrides, 9.0g tellurium dioxide,
The arsenic acid that phosphoric acid that 5.4g uranium dioxide, 43.6g mass concentrations are 85%, 24.7g mass concentrations are 80%, is placed in 98 DEG C of water
It is stirred at reflux in bath 1 hour, adds 3.6g cupric phosphates, 2.0g stannous chlorides and 13.6g copper nitrates, it is small to continue return stirring 10
When after arrive navy blue catalyst precursor solution.
A certain amount of above-mentioned catalyst solution is weighed, which is placed on pneumatic spray drying device spray and is done
Dry, compressed air flow velocity is 8L/min, and the inlet temperature of spray dryer is 130~145 DEG C, and outlet temperature is 73~80 DEG C,
Charging pump speed is 450~500mL/h, and the average grain diameter for obtaining catalyst powder is 4 μm.
It takes 4.2g 1- butyl -3- methylimidazole acetate to be dissolved in the ethyl alcohol that 400g water contents are 5wt% and obtains slurry
(being denoted as slurry A) takes 300g catalyst powders to be dispersed in slurry A, obtains slurry B, and obtained slurry B is sprayed to seed-coating machine
On the alumina balls of a diameter of 1~2mm of 150g of middle progressive rolling movement, in spraying process, the set temperature of seed-coating machine is 60 DEG C, whole
A intermittent spray process takes 30min altogether, obtains coated catalysts.
The coated catalysts of gained are placed in air dry oven 75 DEG C of dryings 5 hours.Again by the catalyst after drying into
Row roasting, stops 2 hours under 370 DEG C of nitrogen atmospheres, is stopped 5 hours under 330 DEG C of air atmospheres.Finally obtain coating catalysis
Agent.
Coated catalysts after above-mentioned roasting are subjected to Analysis of Physical：The load percentage of its catalyst is 42%, mill
It is 1.0% to damage index；The hole contained hole appearance that aperture is 20~1000nm in outer layer active component accounts for the 77% of total pore volume, and aperture is
Kong Rong shared by the hole of 50~500nm accounts for the 41% of total pore volume.
(b) reaction of isobutene gaseous oxidation synthesizing methyl methacrylaldehyde
The obtained coated catalysts of 1.2mL are loaded in the fixed bed reactors that internal diameter is 12mm, above and below catalyst
The quartz sand of the grain sizes such as filling, with methacrolein:Oxygen:Water:Nitrogen=5:9:20:90 (molar ratios) are raw material, air speed
For 1100h-1, it is reaction condition that pressure (absolute pressure), which is 0.15MPa, is reacted 2 hours at 300 DEG C.
Reaction product n-heptanol absorbs and uses gas chromatographic analysis.
The conversion ratio of methacrolein is defined as follows：
[1- be (methacrolein of amount/supply of the substance of unreacted methacrolein by X (methacrolein) %=
The amount of substance)] × 100%
The selectivity of methacrylic acid is defined as follows：
S (methacrylic acid) %=[amounts of the substance of the methacrylic acid of the generation/(substance of the methacrolein of supply
The unreacted methacrolein of amount-substance amount)] × 100%
The conversion ratio for measuring methacrolein is 80.6%, and the selectivity of methacrylic acid is respectively 81.1%.
Embodiment 8
Heteropolyacid catalyst powder is prepared with reference to embodiment 7, then uses following steps prepares coating catalyst：Take 5.0g
Tetraethyl ammonium acetate is dissolved in the ethyl alcohol that 400g water contents are 5wt% and obtains slurry (being denoted as slurry A), takes 250g catalyst powders
Body is dispersed in slurry A, obtains slurry B, by obtained slurry B spray to the 120g a diameter of 1 of progressive rolling movement in seed-coating machine~
On the alumina balls of 2mm, in spraying process, the set temperature of seed-coating machine is 70 DEG C, and entire intermittent spray process takes altogether
40min obtains coated catalysts.
The coated catalysts of gained are placed in air dry oven 75 DEG C of dryings 5 hours.Again by the catalyst after drying into
Row roasting, stops 2 hours under 370 DEG C of nitrogen atmospheres, is stopped 5 hours under 330 DEG C of air atmospheres.Finally obtain coating catalysis
Agent.
Coated catalysts after above-mentioned roasting are subjected to Analysis of Physical：The load percentage of its catalyst is 53%, mill
It is 1.1% to damage index；The hole contained hole appearance that aperture is 20~1000nm in outer layer active component accounts for the 84% of total pore volume, and aperture is
Kong Rong shared by the hole of 50~500nm accounts for the 48% of total pore volume.
The reaction that methacrolein oxidative synthesis methacrylic acid is carried out according to method same as Example 7, at 300 DEG C
Lower reaction 2 hours, the conversion ratio for measuring methacrolein are 89.7%, and the selectivity of methacrylic acid is 86.8%.
Illustrated by above-described embodiment, the preparation method of the coated catalysts is simple, using variety classes and chain length from
Sub- liquid can selectively obtain required aperture and pore-size distribution as binder, and catalyst obtained has higher resistance to
Performance, mechanical strength are ground, and the coated catalysts are propylene oxidation prepares methacrylaldehyde, (methyl) acrolein oxidation prepares (first
Base) acrylic acid tool and isobutylene oxidation prepare methacrolein when have good reactivity.
Claims (10)
1. a kind of using ionic liquid as the preparation method of the coated catalysts of binder, which is characterized in that this method is with ionic liquid
Body is combined by three kinds of co-precipitation, spray drying and spraying methods as binder, it is strong to obtain the easy modulation of pore structure, machinery
Degree is high, uniformity is good, active high and good stability coated catalysts, includes the following steps：
（a）Under certain condition, required dissolving metal salts are mixed and added into precipitating reagent, obtain catalyst pulp, and one
Aging is spare under fixed condition；
（b）Drying process under certain condition（a）Obtained suspension obtains required catalyst powder；
（c）In ethanol by the dispersion of a certain amount of ionic liquid, ionic liquid solution is obtained；
（d）By process（b）Obtained catalyst powder is added to process（c）Obtained ionic liquid solution in, urged
The mixed slurry of agent and ionic liquid；
（e）By process（d）In obtained mixed slurry spray on sphere inert carrier, obtain coated catalysts；
（f）By process（e）In obtain coated catalysts and be placed under certain temperature to be dried；
（g）By process（f）In catalyst after obtained drying be placed in tube furnace and roasted under certain condition.
2. according to claim 1 using ionic liquid as the preparation method of the coated catalysts of binder, which is characterized in that
The outer layer active component of the coated catalysts and the mass ratio of sphere inert carrier are 2~0.1：1.
3. according to claim 1 using ionic liquid as the preparation method of the coated catalysts of binder, which is characterized in that
The outer layer active component of the coated catalysts be Fe, Bi, Co, Ni, Cs, Ce, La, Zr, Sb, Sr, W, Sn, K in one kind or
Two or more elements.
4. according to claim 1 using ionic liquid as the preparation method of the coated catalysts of binder, which is characterized in that
The sphere inert carrier of the coated catalysts is aluminium oxide, pelelith, molecular sieve or red pottery stone, and Carrier diameters are 1~6
mm。
5. according in claim 1 using ionic liquid as the preparation method of the coated catalysts of binder, which is characterized in that institute
The spray dryer inlet temperature for stating spray drying process is 120~240 DEG C, and outlet temperature is 70~160 DEG C.
6. according to claim 1 using ionic liquid as the preparation method of the coated catalysts of binder, which is characterized in that
The ionic liquid selects ion liquid of quaternaries or glyoxaline ion liquid.
7. according to claim 6 using ionic liquid as the preparation method of the coated catalysts of binder, which is characterized in that
The ion liquid of quaternaries general formula is [NRaRbRcRd] Z, glyoxaline ion liquid general formula is [CnMim] Y, wherein a, b,
C, d values 1-4, n value 3-8；Anion Z and Y choose organic acid anions.
8. according to claim 1 using ionic liquid as the preparation method of the coated catalysts of binder, which is characterized in that
It is 30~90 DEG C that the spraying operation, which uses single fluid spray pattern, spraying temperature,.
9. according to, using ionic liquid as the preparation method of the coated catalysts of binder, feature exists described in claim 8
In single fluid composition includes urging in (b) process in preparation method described in ethyl alcohol, water, ionic liquid and claim 1
Agent powder；Wherein, a concentration of 0.5~5 wt% of ionic liquid, water content are≤10 wt%.
10. according to, using ionic liquid as the preparation method of the coated catalysts of binder, feature exists described in claim 1
Prepare methacrylaldehyde for propylene oxidation in, coated catalysts, isobutylene oxidation prepare methacrolein reaction and（First
Base）It is prepared by acrolein oxidation（Methyl）Acrylic acid.
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| CN110560079B (en) * | 2019-07-31 | 2022-01-25 | 浙江新和成股份有限公司 | Catalyst for preparing acrylic acid or acrolein and preparation method thereof |
| CN110420643A (en) * | 2019-08-16 | 2019-11-08 | 中国科学院过程工程研究所 | A kind of preparation method and applications of eggshell type composite metal catalyst |
| 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 |
| CN111403805A (en) * | 2020-04-28 | 2020-07-10 | 深圳先进技术研究院 | Composite solid electrolyte, preparation method thereof and lithium ion battery |
| CN114054100B (en) * | 2020-08-06 | 2023-01-10 | 中国科学院过程工程研究所 | Preparation and application of doped composite oxide catalyst |
| CN114887627B (en) * | 2022-05-14 | 2023-12-12 | 中海油天津化工研究设计院有限公司 | Preparation method of coating catalyst for preparing acrylic acid by acrolein oxidation |
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| WO2012034839A1 (en) * | 2010-09-17 | 2012-03-22 | Jbach Gmbh | Method for catalytically producing formic acid |
| CN102553624A (en) * | 2012-01-05 | 2012-07-11 | 中国科学院过程工程研究所 | Preparation method of catalyst for synthesizing methacrylic acid |
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| CN104801351A (en) * | 2015-04-01 | 2015-07-29 | 万华化学集团股份有限公司 | Preparation method of coating catalyst and coating catalyst prepared by using method |
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