CN107115864B - Bi-component composite alumina high heat stability ordered mesoporous material and preparation method thereof - Google Patents
Bi-component composite alumina high heat stability ordered mesoporous material and preparation method thereof Download PDFInfo
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- CN107115864B CN107115864B CN201710252681.4A CN201710252681A CN107115864B CN 107115864 B CN107115864 B CN 107115864B CN 201710252681 A CN201710252681 A CN 201710252681A CN 107115864 B CN107115864 B CN 107115864B
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- acid
- mesoporous material
- preparation
- aluminium
- nitrate
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- 239000013335 mesoporous material Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 29
- 239000011148 porous material Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 229920001400 block copolymer Polymers 0.000 claims abstract description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 9
- 238000012545 processing Methods 0.000 claims abstract description 8
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 7
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 24
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- 239000004411 aluminium Substances 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 230000008859 change Effects 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- -1 isobutanol aluminum Chemical compound 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 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 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- UCAOGXRUJFKQAP-UHFFFAOYSA-N n,n-dimethyl-5-nitropyridin-2-amine Chemical compound CN(C)C1=CC=C([N+]([O-])=O)C=N1 UCAOGXRUJFKQAP-UHFFFAOYSA-N 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001992 poloxamer 407 Polymers 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- ODPUKHWKHYKMRK-UHFFFAOYSA-N cerium;nitric acid Chemical compound [Ce].O[N+]([O-])=O ODPUKHWKHYKMRK-UHFFFAOYSA-N 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 claims 1
- 230000002209 hydrophobic effect Effects 0.000 claims 1
- 239000004615 ingredient Substances 0.000 claims 1
- 125000003367 polycyclic group Chemical group 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 9
- 238000012512 characterization method Methods 0.000 description 15
- 229960004756 ethanol Drugs 0.000 description 15
- 239000000047 product Substances 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 11
- 210000003850 cellular structure Anatomy 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 5
- ZXTFQUMXDQLMBY-UHFFFAOYSA-N alumane;molybdenum Chemical compound [AlH3].[Mo] ZXTFQUMXDQLMBY-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- WLLURKMCNUGIRG-UHFFFAOYSA-N alumane;cerium Chemical compound [AlH3].[Ce] WLLURKMCNUGIRG-UHFFFAOYSA-N 0.000 description 3
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 3
- QQHSIRTYSFLSRM-UHFFFAOYSA-N alumanylidynechromium Chemical compound [Al].[Cr] QQHSIRTYSFLSRM-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
- 238000000935 solvent evaporation Methods 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009415 formwork Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- YYCNOHYMCOXPPJ-UHFFFAOYSA-N alumane;nickel Chemical compound [AlH3].[Ni] YYCNOHYMCOXPPJ-UHFFFAOYSA-N 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The present invention relates to a kind of bi-component composite alumina high heat stability ordered mesoporous materials, it is that organic carboxyl acid, inorganic acid and block copolymer nonionic surfactant are dissolved in the dehydrated alcohol containing deionized water, silicon source stirring and dissolving is added, under open state after solvent flashing, it is added in metal heteroatom precursor solution, it seals solvent heat grafting under high pressure to handle, product roasts to obtain two-component composite alumina high heat stability ordered mesoporous material after processing.Mesoporous material prepared by the present invention has high-specific surface area and pore volume, structure-controllable, thermal stability height, hole wall acidity and hetero atom active component adjustable, and meso-hole structure high-sequential.
Description
Technical field
The present invention relates to a kind of alumina base mesoporous material, especially a kind of bi-component composite oxygen containing metal heteroatom
Change aluminium mesoporous material and the preparation method of the material.Mesoporous material of the present invention has high-specific surface area and pore volume, knot
Structure is controllable, thermal stability is high, hole wall is acid and metal heteroatom active component is adjustable, and meso-hole structure high-sequential.
Background technique
Mesoporous aluminum oxide material due to good mechanical strength, higher chemical stability, suitable isoelectric point, can
Surface acid/alkalinity of modulation and a variety of different crystal phase structures, become most widely used catalysis in chemical industry and petroleum industry
Agent carrier, in the cracking of petroleum component, hydrofinishing, hydrodesulfurization, the reformation hydrogen production of hydrocarbon, gas phase oil product component
Play an important role in the reaction process such as purifying, purifying vehicle exhaust (Progress in Chemistry, 2010,
22:32.)。
However, the electronegativity due to aluminium is lower, it is easy to carry out necleophilic reaction, causes aluminium salt hydrolytic process extremely complex, and
It is highly prone to the influence of the factors such as acidity in synthetic system, water and relative humidity, causes inorganic aluminium species and organic formwork
(Science. 2005,308:1450. cannot be well matched between agent；Chemical Reviews. 2006, 106:1.；
Journal of the American Chemical Society, 2008, 130:3465.).Therefore, through conventional method system
Jie of standby obtained alumina mesoporous material sees and is mutually generally layer structure or unordered " worm shape hole " structure, and aluminium oxide Jie sees
Mutually extremely unstable, during high-temperature roasting removed template method, meso-hole structure easily collapses, and leads to material specific surface area and hole
Volume significantly reduces (Microporous and Mesoporous Materials. 2010,135:60.).
By the synthetic method of solvent evaporation induced self-assembly, although can effectively improve gained alumina mesoporous material
Mesoscopic structure order and thermal stability (Journal of the American Chemical Society, 2008,
130:3465.), however the hole wall of resulting materials is still mainly made of unformed hydroxy Al.Through traditional infusion process carried metal
During active component, meso-hole structure is easily destroyed, and is easy inside material duct or outer surface generates some gold
Belong to the by-product of oxide, thus unfavorable factor (the Chemistry of for causing material duct to block or react as catalysis
Materials. 2011, 23:1147.)。
Therefore, it how by simple, easy duplicate synthetic method, prepares with high-specific surface area and pore volume, structure
Controllably, thermal stability height, hole wall are rich in metal heteroatom active component and hetero atom component and the acid adjustable bi-component of hole wall
Composite alumina ordered mesoporous material becomes the key points and difficulties studied at present.
Summary of the invention
The object of the present invention is to provide a kind of bi-component composite alumina high heat stability ordered mesoporous material and its preparation sides
Method is urged by introducing metal heteroatom active component in the order, stability and increase for improving existing mesoporous aluminum oxide material
While changing active sites, the corresponding acid site number of modulation carrier hole wall surface and acid strength, preparation have large specific surface area
With pore volume, cellular structure height is regular orderly, stability is high and the acid adjustable mesoporous aluminum oxide material of hole wall, thus effectively
Its activity, selectivity and stability in the catalysis such as catalytic pyrolysis, esterification, acylation, oxidation, denitration reaction is improved, simultaneously
Widen its application range.
Bi-component composite alumina high heat stability ordered mesoporous material of the present invention is to be prepared by the following method
It arrives:
1), according to silicon source: organic carboxyl acid: inorganic acid: dehydrated alcohol: deionized water: block copolymer non-ionic surface is living
Property agent=10~100: 0~30: 20~120: 1000~2500: 100~350: 1 mole charge ratio, by organic carboxyl acid, inorganic
Acid and block copolymer nonionic surfactant are dissolved in the dehydrated alcohol containing deionized water, add silicon source, 20~
60 DEG C of stirrings 6~for 24 hours, obtain clear solution；
2), by the clear solution under 30~60 DEG C of open states solvent flashing, obtain package surfactant and hole
Wall is rich in the alumina mesoporous material of aluminium hydroxyl；
3), according to metal heteroatom presoma: dehydrated alcohol: deionized water=0.1~1: 10~100: 1~10 mole
Metal heteroatom presoma is dissolved in the dehydrated alcohol containing deionized water by charge ratio, obtains metal heteroatom presoma
Solution；
4), according to metal heteroatom presoma: silicon source=0.1~1: 1 mole charge ratio, by the package surface-active
The alumina mesoporous material of agent and hole wall rich in aluminium hydroxyl is added in metal heteroatom precursor solution, in sealing autoclave
In solvent heat grafting 24~48h of processing under the conditions of 80~150 DEG C, product after processing is filtered and is dried；
5), the product after the drying is roasted at 300~800 DEG C to 2~5h, remove surfactant, be prepared
Two-component composite alumina high heat stability ordered mesoporous material.
Wherein, the block copolymer nonionic surfactant is as organic formwork agent, to be with structural formula
EOnPOmEOn's or EOnBOmEOn, using Pluronic F-127 as hydrophilic block, polycyclic oxypropylene or poly- butadiene monoxide as thin
The nonionic block copolymers of water block, wherein n=10~180, m=5~100；EO indicates that oxireme, PO indicate epoxy third
Alkene, BO indicate butadiene monoxide.
In above-mentioned preparation method, the silicon source be aluminium isopropoxide, isobutanol aluminum, tert-butyl alcohol aluminium, aluminum nitrate, aluminium chloride or
Aluminum sulfate.
In above-mentioned preparation method, the inorganic acid is hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid.
In above-mentioned preparation method, the organic carboxyl acid is citric acid, glacial acetic acid, oxalic acid or tartaric acid.
In preparation method of the present invention, the metal heteroatom presoma be zirconium, cobalt, nickel, molybdenum, manganese, iron, chromium, copper,
The soluble-salt of magnesium or cerium.
Preferably, the metal heteroatom presoma is one of following compound: zirconium oxychloride, zirconium nitrate, cobalt nitrate,
Nickel nitrate, ammonium molybdate, manganese sulfate, chromic nitrate, copper nitrate, magnesium nitrate or cerous nitrate.
The preparation method of bi-component composite alumina high heat stability ordered mesoporous material of the present invention be in self assembling process,
By introducing organic carboxyl acid and adjusting the temperature and time of solvent evaporation induced self-assembly, so that the hydrolysis-for controlling silicon source is poly-
Rate is closed, so that material exists on organic and inorganic boundary layer does not occur the aluminium hydroxyl (Al- polymerizeing completely more relatively
OH), by interaction of hydrogen bond and between block copolymer nonionic surfactant micella, high mesoporous of order is formed
Alumina material；Solvent heat graft technology is then used, mesoporous aluminum oxide material is added to dissolved with metal heteroatom activity
In the ethanol solution containing a small amount of deionized water of component, condition is grafted by regulation and control solvent heat, promotes to aoxidize aluminium
Because polymerization reaction occurs between metal heteroatom component hydroxyl caused by hydrolysis in aluminium hydroxyl and solution in material hole wall, thus success
Realize that high uniformity grafts in aluminium oxide mesoporous wall on atomic level by metal heteroatom active component, effectively avoids passing
During unified step solvent evaporation induced self-assembly, because rate of polymerization is different is led for metal heteroatom presoma and silicon source hydrolysis-
The problem of synthetic product of cause is the mixture of metal heteroatom oxide and aluminium oxide, is prepared bi-component composite alumina
High heat stability ordered mesoporous material.
The bi-component composite alumina high heat stability ordered mesoporous material being prepared using the above-mentioned preparation method of the present invention
Not only six side of two dimension with high-sequential or three-dimensional cubic meso-hole structure, biggish specific surface and pore volume, and the miscellaneous original of metal
Sub- active component and its content are adjustable, and material hole wall acid site number and acid strength are controllable.Through detecting, the ratio of the mesoporous material
Surface area is 200~450m2/ g, 0.3~1.5cm of pore volume3/ g, mesoporous pore size is adjustable within the scope of 4.0~15.0nm, metal
The molar ratio of hetero atom and aluminium can be adjusted in the range of 0.1~1.
Bi-component composite alumina mesoporous material thermal stability also with higher prepared by the present invention, through 1000 DEG C of high temperature
After roasting, the structural behaviour of material does not change.
Preparation process of the present invention is simple and easy to do, and fidelity factor is high.It is not only cheap and easy to get using organic carboxyl acid as additive, and
And non-toxic, no pollution to the environment.In preparation process, the introducing of metal heteroatom active component does not cause the mesoporous knot of aluminium oxide
The destruction of structure and the blocking of mesopore orbit.
The mesoporous wall of bi-component composite alumina mesoporous material prepared by the present invention is with metal heteroatom-Al combined oxidation
Object form composition, as catalyst, in acid catalyzed reaction, hydrocarbon selective oxidation reaction, oxidative dehydrogenation
And good catalytic activity and stability are shown in the fields such as hydrocarbon selective Reduction of NO reaction.
Detailed description of the invention
Fig. 1 is cobalt-aluminium composite oxide mesoporous material XRD spectra prepared by embodiment 1.
Fig. 2 is that cobalt-aluminium composite oxide mesoporous material element maps map.
Fig. 3 is that cobalt-aluminium composite oxide mesoporous material N2 adsorption-desorption isotherm (A) and corresponding pore-size distribution are bent
Line (B).
Specific embodiment
Below with reference to embodiment, further description of the specific embodiments of the present invention.Following embodiment is only used for more
Technical solution of the present invention is clearly demonstrated, rather than is limited the scope of the invention.Those of ordinary skill in the art are not
In the case where being detached from the principle of the invention and objective, various change, modification, replacement and variant for the progress of these embodiments,
It should be included within protection scope of the present invention.
Embodiment 1.
Take 6.5g EO106PO70EO106, 0.7g citric acid is added 40mL and contains the ethanol solution of 3.5g 12M hydrochloric acid
In, it is stirred at room temperature to being completely dissolved, then 0.032mol aluminium isopropoxide is added into system, after 30 DEG C of stirrings for 24 hours, gained is clarified
Solution pours into culture dish, and solvent flashing handles 48h at 45 DEG C；Then, obtained solid is added to 30mL and contains 0.005mol
In cobalt nitrate and the ethanol solution of 1g deionized water, solvent heat grafting is handled for 24 hours at 100 DEG C in sealing autoclave
Afterwards, it filters, dry, 650 DEG C of roasting 5h obtain cobalt-aluminium composite oxide mesoporous material.
Fig. 1 gives the above-mentioned XRD spectra for preparing sample.As seen from the figure, resulting materials are shown respectively in 0.92 ° and 1.57 °
One strong diffraction maximum and a relatively weak diffraction maximum are shown.It is carried out by the inverse to interplanar distance corresponding to diffraction maximum
It calculates, it was demonstrated that the sample has the hexagonal mesoporous structure of two dimension of high-sequential.
The element mapping pattern analysis results of Fig. 2 further confirm that Al/Co atomic ratio is 6.5: 1 in sample, and Al, Co
Species can reach the dispersion of the high uniformity on atomic level in entire sample scope.
Fig. 3 gives the N2 adsorption-desorption isotherm (A) and corresponding pore size distribution curve (B) of sample.It can according to Fig. 3
To find out, which shows the typical IV type adsorption isotherm of columnar hole and H1 type hysteresis loop, and is 0.62 in relative pressure
A more precipitous capillary condensation curve is shown in~0.80 range, shows that the sample has the meso-hole structure of high-sequential
And mesoporous Kong Jing larger and that distribution is uniform.By being calculated, the mesoporous pore size of sample is 8.6nm, specific surface area 260m2/
G, pore volume 0.54cm3/g。
Gained sample after high-temperature roasting processing 1h, is measured into every physical and chemical indexes of sample, display at 1000 DEG C again
Sample structure performance does not change.
Cobalt manufactured in the present embodiment-aluminium composite oxide mesoporous material 0.05g is taken, 15mL is added together with 1.0g styrene
In Isosorbide-5-Nitrae-dioxane solution, the rate at 90 DEG C with 12mL/min is passed through oxygen, carries out epoxidation of styrene and reacts 5h.Catalysis
Reaction result shows that cobalt-aluminium composite oxide mesoporous material can reach 80.6% to the conversion ratio of styrene, and epoxy in product
The selectivity of vinylbenzene is 59.3%.
Above-mentioned cobalt-aluminium composite oxide mesoporous material is recycled and reused for epoxidation of styrene reaction, is reused three times
Later, almost unchanged to the activity of conversion of styrene and selectivity of product.
Embodiment 2.
Take 6.5g EO106PO70EO106, 0.6g oxalic acid, be added 40mL contain in the ethanol solution of 2.5g 2M phosphoric acid,
It is stirred at room temperature to being completely dissolved, then is added 0.045mol tert-butyl alcohol aluminium into system, after 40 DEG C of stirring 12h, gained is clarified molten
Liquid pours into culture dish, and solvent flashing handles 48h at 50 DEG C；Then, obtained solid is added to 20mL and contains 0.006mol nitre
In sour chromium and the ethanol solution of 0.5g deionized water, solvent heat grafting is handled for 24 hours at 120 DEG C in sealing autoclave
Afterwards, it filters, dry, 550 DEG C of roasting 5h obtain chromium-aluminium composite oxide mesoporous material.
XRD characterization is the result shows that prepared sample shows the hexagonal mesoporous cellular structure of two dimension of high-sequential, and Cr object
Kind high uniformity can be scattered in mesoporous wall on atomic level.It is measured through SEM-EDX, Al/Cr atomic ratio is in sample
7.3∶1。
N2 adsorption characterization result shows that gained chromium-aluminium composite oxide mesoporous material mesoporous pore size is 8.7nm, compares table
Area is 220m2/ g, pore volume 0.49cm3/g.Sample is roasted into 1h at 1000 DEG C, structural behaviour does not change.
Take 0.1g chromium-aluminium composite oxide mesoporous material, 10mL acetonitrile, 2mL hexamethylene and 3mL hydrogen peroxide that reaction is added
In kettle, 4h is reacted at 80 DEG C.Cyclohexane selectivity catalytic oxidation Evaluation results show resulting materials to hexamethylene
Conversion ratio can reach 15.1%, and the selectivity of cyclohexanol and cyclohexanone is respectively 75.9 and 24.1% in product.It is repeated three times
After use, mesoporous material is almost unchanged to the activity of conversion and selectivity of product of hexamethylene.
Embodiment 3.
Take 8.1g EO106PO70EO106, 0.8g glacial acetic acid is added 40mL and contains the ethanol solution of 2.6g 12M hydrochloric acid
In, it is stirred at room temperature to being completely dissolved, then 0.035mol aluminium chloride is added into system, after 38 DEG C of stirrings for 24 hours, gained is clarified molten
Liquid pours into culture dish, and solvent flashing handles 48h at 45 DEG C；Then, obtained solid is added to 20mL and contains 0.003mol molybdenum
In sour ammonium and the ethanol solution of 0.5g deionized water, solvent heat grafting is handled for 24 hours at 100 DEG C in sealing autoclave
Afterwards, it filters, dry, 550 DEG C of roasting 5h obtain molybdenum-aluminium composite oxide mesoporous material.
XRD characterization is the result shows that prepared sample shows the hexagonal mesoporous cellular structure of two dimension of high-sequential, and Mo object
Kind high uniformity can be scattered in mesoporous wall on atomic level.It is measured through SEM-EDX, Al/Mo atomic ratio is in sample
10.8∶1。
N2 adsorption characterization result shows that gained molybdenum-aluminium composite oxide mesoporous material mesoporous pore size is 8.2nm, compares table
Area is 280m2/ g, pore volume 0.56cm3/g.Sample is roasted into 1h at 1000 DEG C, structural behaviour does not change.
NH3- TPD characterization result shows that gained molybdenum-aluminium composite oxide mesoporous material surface total acid content reaches
2.12mmole/g, middle strong acidity position content reach 35.2%.
Molybdenum-aluminium composite oxide mesoporous material of the 0.5g after 200 DEG C of activation is taken, is filled in fixed-bed micro-reactor,
It is passed through alcohol vapour, carries out Dehydrogenating reaction of alcohol 1h at 350 DEG C.Reaction result shows that resulting materials are to Dehydrogenating reaction of alcohol
High conversion rate is up to 89.2%, and the selectivity of ethylene reaches 96.5% in product.
Embodiment 4.
Take 3.6g EO30PO70EO30Be added 40mL contain in the ethanol solution of 3.0g 12M hydrochloric acid, be stirred at room temperature to
It is completely dissolved, then 0.032mol aluminium isopropoxide is added into system, after 40 DEG C of stirrings for 24 hours, gained clear solution is poured into culture
In ware, solvent flashing is handled for 24 hours at 60 DEG C；Then, obtained solid is added to 20mL and contains 0.004mol cerous nitrate and 0.5g
In the ethanol solution of deionized water, filters, do after solvent heat grafting processing for 24 hours at 100 DEG C in sealing autoclave
Dry, 450 DEG C of roasting 5h obtain cerium-aluminium composite oxide mesoporous material.
XRD characterization is the result shows that prepared sample shows the hexagonal mesoporous cellular structure of two dimension of high-sequential.SEM-EDX
Characterization result further confirms that Al/Ce atomic ratio is 8.1: 1 in sample, and Al, Ce species can reach height on atomic level
It is evenly dispersed.
N2 adsorption characterization result shows that gained cerium-aluminium composite oxide mesoporous material mesoporous pore size is 5.2nm, compares table
Area is 348m2/ g, pore volume 0.45cm3/g.Sample is roasted into 1h at 1000 DEG C, structural behaviour does not change.
0.1g cerium-aluminium composite oxide mesoporous material, 10mL acetonitrile, 3mL hexamethylene and 5mL tert-butyl hydroperoxide is taken to add
Enter in reaction kettle, reacts 4h at 80 DEG C.Cyclohexane selectivity catalytic oxidation Evaluation results show resulting materials to ring
The conversion ratio of hexane can reach 12.1%, and the selectivity of cyclohexanol and cyclohexanone is respectively 38.9 and 52.4% in product.Through three
After secondary reuse, mesoporous material is almost unchanged to the activity of conversion and selectivity of product of hexamethylene.
Embodiment 5.
Take 4.6g EO39BO47EO39, 0.6g citric acid, be added 40mL contain in the ethanol solution of 2.0g 2M sulfuric acid,
It is stirred at room temperature to being completely dissolved, then 0.040mol isobutanol aluminum is added into system, after 45 DEG C of stirrings for 24 hours, gained is clarified molten
Liquid pours into culture dish, and solvent flashing is handled for 24 hours at 60 DEG C；Then, obtained solid is added to 30mL and contains 0.003mol nitre
In sour nickel and the ethanol solution of 2g deionized water, solvent heat grafting is handled for 24 hours at 120 DEG C in sealing autoclave
Afterwards, it filters, dry, 550 DEG C of roasting 5h obtain nickel-aluminum composite oxides mesoporous material.
XRD characterization is the result shows that prepared sample shows the hexagonal mesoporous cellular structure of two dimension of high-sequential, and hole wall
Interior Ni, Al species reach the dispersion of the high uniformity on atomic level.It is measured through SEM-EDX, Al/Ni atomic ratio is 13.5 in sample
∶1。
N2 adsorption characterization result shows that the mesoporous pore size of gained nickel-aluminum composite oxides mesoporous material is 5.2nm, compares table
Area is 352m2/ g, pore volume 0.47cm3/g.Sample is roasted into 1h at 1000 DEG C, structural behaviour does not change.
Take 0.5g through H2Nickel-aluminum composite oxides mesoporous material after 600 DEG C of activation, is filled in fixed-bed micro-reactor
It is interior, it is passed through the mixed gas that methane and oxygen molar ratio are 2, methane synthesis gas reaction, time 1h are carried out at 600 DEG C.Instead
Answer the results show that resulting materials to the conversion ratio of methane up to 85.2%, carbon monoxide yield is up to 89.6% in product.
Embodiment 6.
Take 4.2g EO27PO61EO27, 1.6g glacial acetic acid, be added 40mL contain in the ethanol solution of 2.0g 6M hydrochloric acid,
It is stirred at room temperature to being completely dissolved, then 0.038mol aluminum nitrate is added into system, after 30 DEG C of stirrings for 24 hours, by gained clear solution
It pours into culture dish, solvent flashing handles 48h at 60 DEG C；Then, obtained solid is added to 20mL and contains 0.003mol sulfuric acid
In manganese and the ethanol solution of 2g deionized water, in sealing autoclave at 100 DEG C after solvent heat grafting processing for 24 hours,
It filters, dry, 650 DEG C of roasting 5h obtain manganese-aluminium composite oxide mesoporous material.
The result shows that prepared sample has the hexagonal mesoporous cellular structure of two dimension, SEM-EDX characterization confirms XRD characterization, should
Mn, Al species reach the dispersion of the high uniformity on atomic level in material mesoporous wall, and wherein Al/Mn atomic ratio reaches 12.8:
1。
N2 adsorption characterization result shows that gained manganese-aluminium composite oxide mesoporous material has uniform mesoporous pore size, average
Mesoporous pore size is 4.9nm, specific surface area 392m2/ g, pore volume 0.44cm3/g.Sample is roasted into 1h at 1000 DEG C, is tied
Structure performance does not change.
Take 0.25g manganese-aluminium composite oxide mesoporous material to be filled in fixed-bed micro-reactor, under He atmosphere with 5 DEG C/
The heating rate of min rises to 550 DEG C from room temperature, is passed through containing NO (0.25%)-CH4(0.28%)-O2(3%) He gas carries out CH4It urges
Change reduction NO reaction, reaction time 1h.Reaction result shows that under excess oxygen, resulting materials are to CH4With the conversion ratio point of NO
96.2% and 58.2% are not can reach.
Embodiment 7.
Take 7.2g EO106PO70EO106, 0.6g citric acid is added 40mL and contains the ethanol solution of 2.6g 2M nitric acid
In, it is stirred at room temperature to being completely dissolved, then 0.042mol aluminum sulfate is added into system, after 40 DEG C of stirrings for 24 hours, gained is clarified molten
Liquid pours into culture dish, and solvent flashing handles 48h at 50 DEG C；Then, obtained solid is added to 35mL and contains 0.005mol nitre
In sour copper and the ethanol solution of 0.8g deionized water, solvent heat grafting is handled for 24 hours at 120 DEG C in sealing autoclave
Afterwards, it filters, dry, 650 DEG C of roasting 5h obtain copper-aluminium composite oxide mesoporous material.
XRD characterization is the result shows that prepared sample shows that the hexagonal mesoporous cellular structure of two dimension of high-sequential and height are equal
One mesoporous pore size, and Cu species high uniformity can be scattered in aluminium oxide mesoporous wall on atomic level, Al/Cu atomic ratio
It is 8.6: 1.
N2 adsorption characterization result shows that gained copper-aluminium composite oxide mesoporous material mesoporous pore size is 7.8nm, compares table
Area is 286m2/ g, pore volume 0.55cm3/g.Sample is roasted into 1h at 1000 DEG C, structural behaviour does not change.
Take 0.5g copper-aluminium composite oxide mesoporous material to be filled in fixed-bed micro-reactor, under He atmosphere with 20 DEG C/
The heating rate of min rises to 350 DEG C from room temperature, is passed through containing NO (0.5%)-C3H6(0.5%)-O2(3%) He gas carries out C3H6Catalysis
Restore NO reaction, reaction time 1h.Reaction result shows that resulting materials are to C3H682.2% He is respectively reached with the conversion ratio of NO
56.3%。
Claims (9)
1. a kind of preparation method of bi-component composite alumina high heat stability ordered mesoporous material, the method is as steps described below
It carries out:
1), according to silicon source: organic carboxyl acid: inorganic acid: dehydrated alcohol: deionized water: block copolymer nonionic surfactant=
10~100: 0~30: 20~120: 1000~2500: 100~350: 1 mole charge ratio, by organic carboxyl acid, inorganic acid and embedding
Section copolymer nonionic surfactant is dissolved in the dehydrated alcohol containing deionized water, adds silicon source, 20~60 DEG C are stirred
Mix 6~for 24 hours, obtain clear solution；
2), by the clear solution under 30~60 DEG C of open states solvent flashing, obtain package surfactant and hole wall be rich
The alumina mesoporous material of the hydroxyl containing aluminium；
3), according to metal heteroatom presoma: dehydrated alcohol: deionized water=0.1~1: 10~100: 1~10 mole ingredient
Than metal heteroatom presoma is dissolved in the dehydrated alcohol containing deionized water, metal heteroatom precursor solution is obtained；
4), according to metal heteroatom presoma: silicon source=0.1~1: 1 mole charge ratio, by the package surfactant and
Alumina mesoporous material of the hole wall rich in aluminium hydroxyl is added in metal heteroatom precursor solution, 80 in sealing autoclave
Solvent heat grafting 24~48h of processing, product after processing is filtered and is dried under the conditions of~150 DEG C；
5), the product after the drying is roasted at 300~800 DEG C to 2~5h, remove surfactant, double groups are prepared
Part composite alumina high heat stability ordered mesoporous material.
2. preparation method according to claim 1, it is characterized in that the block copolymer nonionic surfactant is
It is EOnPOmEOn or EOnBOmEOn with structural formula, using Pluronic F-127 as hydrophilic block, polycyclic oxypropylene or polycyclic
Nonionic block copolymers of the oxygen butylene as hydrophobic block, wherein n=10~180, m=5~100；EO indicates oxireme,
PO indicates that propylene oxide, BO indicate butadiene monoxide.
3. preparation method according to claim 1, it is characterized in that the silicon source is aluminium isopropoxide, isobutanol aluminum, tertiary fourth
Aluminium alcoholates, aluminum nitrate, aluminium chloride or aluminum sulfate.
4. preparation method according to claim 1, it is characterized in that the inorganic acid is hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid.
5. preparation method according to claim 1, it is characterized in that the organic carboxyl acid is citric acid, glacial acetic acid, oxalic acid
Or tartaric acid.
6. preparation method according to claim 1, it is characterized in that the metal heteroatom presoma be zirconium, cobalt, nickel,
Molybdenum, manganese, iron, chromium, copper, magnesium or cerium soluble-salt.
7. preparation method according to claim 6, it is characterized in that the metal heteroatom presoma is following compound
One of: zirconium oxychloride, zirconium nitrate, cobalt nitrate, nickel nitrate, ammonium molybdate, manganese sulfate, chromic nitrate, copper nitrate, magnesium nitrate or nitric acid
Cerium.
8. the bi-component composite alumina high heat stability ordered mesoporous material that preparation method described in claim 1 is prepared, institute
State two dimension hexagonal mesoporous structure of the material with high-sequential, 200~450m of specific surface area2/ g, 0.3~1.5cm of pore volume3/ g,
The molar ratio of 4.0~15.0nm of mesoporous pore size, metal heteroatom and aluminium is adjusted in the range of 0.1~1.
9. bi-component composite alumina high heat stability ordered mesoporous material described in claim 8 is as hydrocarbon selectivity oxygen
Change the application of reaction, oxidative dehydrogenation or the anti-applications catalyst of hydrocarbon selective Reduction of NO.
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| WO2015126236A1 (en) * | 2014-02-18 | 2015-08-27 | Universidad Nacional Autónoma de México | Method for obtaining a composite aluminosilicate material containing alumina and nanozeolite |
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