CN107115864A - 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
- Publication number
- CN107115864A CN107115864A CN201710252681.4A CN201710252681A CN107115864A CN 107115864 A CN107115864 A CN 107115864A CN 201710252681 A CN201710252681 A CN 201710252681A CN 107115864 A CN107115864 A CN 107115864A
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- China
- Prior art keywords
- acid
- mesoporous material
- preparation
- aluminium
- heat stability
- Prior art date
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- Granted
Links
- 239000013335 mesoporous material Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 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 26
- 238000002360 preparation method Methods 0.000 title claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000011148 porous material Substances 0.000 claims abstract description 33
- 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
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 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
- 238000012545 processing Methods 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- 229920001400 block copolymer Polymers 0.000 claims abstract description 8
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 8
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 23
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- 239000004411 aluminium Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 238000000967 suction filtration 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
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 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
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- -1 isobutanol aluminum Chemical compound 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 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
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 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
- 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
- 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
- 239000003054 catalyst Substances 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
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052802 copper Inorganic materials 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
- 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 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-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
- 239000006227 byproduct Substances 0.000 claims description 2
- 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 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
- 229920001577 copolymer Polymers 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
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 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
- ODPUKHWKHYKMRK-UHFFFAOYSA-N cerium;nitric acid Chemical compound [Ce].O[N+]([O-])=O ODPUKHWKHYKMRK-UHFFFAOYSA-N 0.000 claims 1
- 230000002209 hydrophobic effect Effects 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 description 25
- 235000019441 ethanol Nutrition 0.000 description 18
- 238000012512 characterization method Methods 0.000 description 14
- 235000010210 aluminium Nutrition 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 11
- 230000008859 change Effects 0.000 description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 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
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 235000015165 citric acid Nutrition 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
- 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
- 239000003795 chemical substances by application 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
- WLLURKMCNUGIRG-UHFFFAOYSA-N alumane;cerium Chemical compound [AlH3].[Ce] WLLURKMCNUGIRG-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 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
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 235000016768 molybdenum Nutrition 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000003643 water by type Substances 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
- 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
- 230000004913 activation Effects 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
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-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
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 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 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
- 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
- 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
- 239000000203 mixture Substances 0.000 description 1
- 150000002823 nitrates Chemical class 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
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method 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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Abstract
The present invention relates to a kind of bi-component composite alumina high heat stability ordered mesoporous material, it is that organic carboxyl acid, inorganic acid and block copolymer nonionic surfactant are dissolved in the absolute ethyl alcohol containing deionized water, add silicon source stirring and dissolving, under open state after solvent flashing, add in metal heteroatom precursor solution, seal solvent heat grafting under high pressure to handle, product roasting obtains 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, heat endurance 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, particularly a kind of bi-component composite oxygen containing metal heteroatom
Change aluminium mesoporous material, and the material preparation method.Mesoporous material of the present invention has high-specific surface area and pore volume, knot
Structure is controllable, heat endurance is high, hole wall is acid and metal heteroatom active component is adjustable, and meso-hole structure high-sequential.
Background technology
Mesoporous aluminum oxide material due to good mechanical strength, higher chemical stability, suitable isoelectric point, can
The surface acid of modulation/alkaline and a variety of different crystal phase structures, as 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
Played an important role in the courses of reaction such as purifying, purifying vehicle exhaust (Progress in Chemistry, 2010,
22:32.)。
However, because the electronegativity of aluminium is relatively low, easily carrying out necleophilic reaction, cause aluminium salt hydrolytic process extremely complex, and
The influence of the factors such as acidity in synthetic system, water and relative humidity is highly prone to, inorganic aluminium species and organic formwork is caused
(Science. 2005,308 can not be well matched between agent:1450.;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 aluminum oxide Jie sees
Mutually extremely unstable, during high-temperature roasting removed template method, meso-hole structure easily caves in, and causes material specific surface area and hole
Volume significantly reduces (Microporous and Mesoporous Materials. 2010,135:60.).
Pass through the synthetic method of solvent evaporation induced self-assembly, although gained alumina mesoporous material can be effectively improved
Mesoscopic structure order and heat endurance (Journal of the American Chemical Society, 2008,
130:3465.), however the hole wall of resulting materials is still mainly made up of unformed hydroxy Al.Through traditional infusion process carried metal
During active component, its meso-hole structure easily be destroyed, and easily inside material duct or outer surface produce some gold
Belong to the accessory substance of oxide, so as to cause material duct to block or unfavorable factor (the Chemistry of as catalytic reaction
Materials. 2011, 23:1147.)。
Therefore, how by synthetic method that is simple, easily repeating, prepare with high-specific surface area and pore volume, structure
Controllable, heat endurance is high, hole wall is rich in metal heteroatom active component and hetero atom component and the acid adjustable bi-component of hole wall
Composite alumina ordered mesoporous material, as the emphasis and difficult point studied at present.
The content of the invention
It is an object of the invention to provide a kind of bi-component composite alumina high heat stability ordered mesoporous material and its preparation side
Method, by introducing metal heteroatom active component, is urged 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, preparing has large specific surface area
With pore volume, pore passage structure highly it is regular in order, stability is high and the acid adjustable mesoporous aluminum oxide material of hole wall, so that effectively
Its activity, selectivity and stability in the catalytic reactions such as catalytic pyrolysis, esterification, acylation, oxidation, denitration is improved, simultaneously
Widen its application.
Bi-component composite alumina high heat stability ordered mesoporous material of the present invention is to be prepared into by the following method
Arrive:
1), according to silicon source: organic carboxyl acid: inorganic acid: absolute ethyl 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 absolute ethyl alcohol containing deionized water, adds silicon source, 20~60 DEG C are stirred
6~24h is mixed, settled solution is obtained;
2), by the settled solution under 30~60 DEG C of open states solvent flashing, obtain parcel surfactant and hole wall be rich
The alumina mesoporous material of the hydroxyl containing aluminium;
3), according to metal heteroatom presoma: absolute ethyl alcohol: deionized water=0.1~1: 10~100: 1~10 mole dispensing
Than metal heteroatom presoma is dissolved in the absolute ethyl 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 it is described parcel 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 handles 24~48h under the conditions of~150 DEG C, by product suction filtration and drying after processing;
5) the dried product, is calcined 2~5h at 300~800 DEG C, surfactant is removed, double groups are prepared
Part composite alumina high heat stability ordered mesoporous material.
Wherein, described block copolymer nonionic surfactant is as organic formwork agent, to be with structural formula
EOnPOmEOn, or EOnBOmEOn, using Pluronic F-127 as hydrophilic block, polycyclic oxypropylene or poly- butadiene monoxide be as dredging
The nonionic block copolymers of water block, wherein n=10~180, m=5~100;EO represents oxireme, and PO represents epoxy third
Alkene, BO represents butadiene monoxide.
In above-mentioned preparation method, described silicon source is aluminium isopropoxide, isobutanol aluminum, tert-butyl alcohol aluminium, aluminum nitrate, aluminium chloride or
Aluminum sulfate.
In above-mentioned preparation method, described inorganic acid is hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid.
In above-mentioned preparation method, described organic carboxyl acid is citric acid, glacial acetic acid, oxalic acid or tartaric acid.
In preparation method of the present invention, described metal heteroatom presoma is zirconium, cobalt, nickel, molybdenum, manganese, iron, chromium, copper,
The soluble-salt of magnesium or cerium.
Preferably, described 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 as to control the hydrolysis of silicon source-poly-
Close speed so that material exists on organic and inorganic boundary layer and the aluminium hydroxyl (Al- polymerizeing completely does not more occur 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 and is dissolved with metal heteroatom activity
In the ethanol solution containing a small amount of deionized water of component, by adjusting and controlling solvent heat grafting condition, promote to aoxidize aluminium
Expect in hole wall in aluminium hydroxyl and solution because occurring polymerisation between the metal heteroatom component hydroxyl produced by hydrolysis, so that success
Realize that high uniformity is grafted in aluminum oxide mesoporous wall on atomic level by metal heteroatom active component, is prevented effectively from biography
During unified step solvent evaporation induced self-assembly, because metal heteroatom presoma and silicon source hydrolysis-rate of polymerization is different are led
The problem of synthetic product of cause is the mixture of metal heteroatom oxide and aluminum oxide, prepares bi-component composite alumina
High heat stability ordered mesoporous material.
The bi-component composite alumina high heat stability ordered mesoporous material prepared using above-mentioned preparation method of the invention
Not only two-dimentional six side with high-sequential or three-dimensional cubic meso-hole structure, larger ratio 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.After testing, 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 in the range of 4.0~15.0nm, metal
The mol ratio of hetero atom and aluminium can be adjusted in the range of 0.1~1.
Bi-component composite alumina mesoporous material prepared by the present invention also has higher heat endurance, 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 it is non-toxic, it is environmentally safe.In preparation process, the introducing of metal heteroatom active component does not cause the mesoporous knot of aluminum 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 oxidations
Thing form is constituted, as catalyst, in acid catalyzed reaction, hydrocarbon selective oxidation reaction, oxidative dehydrogenation
And hydrocarbon selective Reduction of NO reaction etc. shows good catalytic activity and stability in field.
Brief description of the drawings
Fig. 1 is the XRD spectra of cobalt-aluminium composite oxide mesoporous material prepared by embodiment 1.
Fig. 2 maps collection of illustrative plates for the element of cobalt-aluminium composite oxide mesoporous material.
Fig. 3 is bent for the N2 adsorption-desorption isotherm (A) and corresponding pore-size distribution of cobalt-aluminium composite oxide mesoporous material
Line (B).
Embodiment
The embodiment of the present invention is further described with reference to embodiment.Following examples are only used for more
Technical scheme is clearly demonstrated, rather than is limited the scope of the invention.Those of ordinary skill in the art are not
In the case of departing from the principle of the invention and objective, various change, modification, replacement and the modification carried out for these embodiments,
It should be included within protection scope of the present invention.
Embodiment 1.
Take 6.5g EO106PO70EO106, 0.7g citric acids add 40mL and contain the ethanol solution of 3.5g 12M hydrochloric acid
In, it is stirred at room temperature to being completely dissolved, then added into system after 0.032mol aluminium isopropoxides, 30 DEG C of stirring 24h, gained is clarified
Solution is poured into culture dish, and solvent flashing handles 48h at 45 DEG C;Then, gained solid is added to 30mL and contains 0.005mol
In cobalt nitrate and the ethanol solution of 1g deionized waters, the solvent heat grafting processing 24h at 100 DEG C in sealing autoclave
Afterwards, suction filtration, is dried, 650 DEG C of roasting 5h, obtains cobalt-aluminium composite oxide mesoporous material.
Fig. 1 gives the above-mentioned XRD spectra for preparing sample.As seen from the figure, resulting materials show respectively at 0.92 ° and 1.57 °
One strong diffraction maximum and a relatively weak diffraction maximum are shown.Carried out by the inverse to interplanar distance corresponding to diffraction maximum
Calculate, it was demonstrated that the sample has the two-dimentional hexagonal mesoporous structure of high-sequential.
Fig. 2 element mapping pattern analysis results further confirm that Al/Co atomic ratios are 6.5: 1 in sample, and Al, Co
Species can reach that the high uniformity on atomic level disperses in whole sample scope.
Fig. 3 gives the N2 adsorption-desorption isotherm (A) and corresponding pore size distribution curve (B) of sample.Can according to Fig. 3
To find out, the sample shows the typical IV types adsorption isotherm of cylinder hole and H1 type hysteresis loops, and is 0.62 in relative pressure
A more precipitous capillary condensation curve is shown in the range of~0.80, shows that the sample has the meso-hole structure of high-sequential
And the larger and homogeneous mesoporous Kong Jing of distribution.By calculating, the mesoporous pore size of sample is 8.6nm, specific surface area 260m2/
G, pore volume 0.54cm3/g。
By gained sample, high-temperature roasting is handled after 1h at 1000 DEG C, again every physical and chemical indexes of determination sample, display
Sample structure performance does not change.
Cobalt manufactured in the present embodiment-aluminium composite oxide mesoporous material 0.05g is taken, 15mL is together added with 1.0g styrene
In Isosorbide-5-Nitrae-dioxane solution, oxygen is passed through with 12mL/min speed at 90 DEG C, epoxidation of styrene reaction 5h is carried out.Catalysis
Reaction result shows, 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, through three reuses
Afterwards, its activity of conversion and selectivity of product to styrene is almost unchanged.
Embodiment 2.
Take 6.5g EO106PO70EO106, 0.6g oxalic acid, add 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 into system after 0.045mol tert-butyl alcohol aluminium, 40 DEG C of stirring 12h, gained is clarified molten
Liquid is poured into culture dish, and solvent flashing handles 48h at 50 DEG C;Then, gained solid is added to 20mL and contains 0.006mol nitre
In the ethanol solution of sour chromium and 0.5g deionized water, the solvent heat grafting processing 24h at 120 DEG C in sealing autoclave
Afterwards, suction filtration, is dried, 550 DEG C of roasting 5h, obtains chromium-aluminium composite oxide mesoporous material.
XRD characterization results show that prepared sample shows the two-dimentional hexagonal mesoporous pore passage structure of high-sequential, and Cr things
Plant high uniformity can be scattered in mesoporous wall on atomic level.Determined through SEM-EDX, Al/Cr atomic ratios are in sample
7.3∶1。
N2 adsorption characterization result shows that the mesoporous pore size of gained chromium-aluminium composite oxide mesoporous material is 8.7nm, compares table
Area is 220m2/ g, pore volume is 0.49cm3/g.Sample is calcined 1h at 1000 DEG C, structural behaviour does not change.
0.1g chromium-aluminium composite oxide mesoporous material, 10mL acetonitriles, 2mL hexamethylenes and 3mL hydrogen peroxide is taken to add reaction
In kettle, 4h is reacted at 80 DEG C.Cyclohexane selectivity catalytic oxidation Evaluation results show that resulting materials are to hexamethylene
Conversion ratio can reach 15.1%, and the selectivity of cyclohexanol and cyclohexanone is respectively 75.9 and 24.1% in product.Through three repetitions
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 adds 40mL and contains the ethanol solution of 2.6g 12M hydrochloric acid
In, it is stirred at room temperature to being completely dissolved, then added into system after 0.035mol aluminium chloride, 38 DEG C of stirring 24h, gained is clarified molten
Liquid is poured into culture dish, and solvent flashing handles 48h at 45 DEG C;Then, gained solid is added to 20mL and contains 0.003mol molybdenums
In the ethanol solution of sour ammonium and 0.5g deionized water, the solvent heat grafting processing 24h at 100 DEG C in sealing autoclave
Afterwards, suction filtration, is dried, 550 DEG C of roasting 5h, obtains molybdenum-aluminium composite oxide mesoporous material.
XRD characterization results show that prepared sample shows the two-dimentional hexagonal mesoporous pore passage structure of high-sequential, and Mo things
Plant high uniformity can be scattered in mesoporous wall on atomic level.Determined through SEM-EDX, Al/Mo atomic ratios are in sample
10.8∶1。
N2 adsorption characterization result shows that the mesoporous pore size of gained molybdenum-aluminium composite oxide mesoporous material is 8.2nm, compares table
Area is 280m2/ g, pore volume is 0.56cm3/g.Sample is calcined 1h at 1000 DEG C, structural behaviour does not change.
NH3- TPD characterization results show that the surface total acid content of gained molybdenum-aluminium composite oxide mesoporous material reaches
2.12mmole/g, its middle strong acidity position content reaches 35.2%.
Molybdenum-aluminium composite oxide mesoporous materials of the 0.5g after 200 DEG C of activation is taken, is filled in fixed-bed micro-reactor,
It is passed through at alcohol vapour, 350 DEG C and carries out Dehydrogenating reaction of alcohol 1h.Reaction result shows that resulting materials are to Dehydrogenating reaction of alcohol
High conversion rate is up to 89.2%, and the selectivity of ethene reaches 96.5% in product.
Embodiment 4.
Take 3.6g EO30PO70EO30Add 40mL contain in the ethanol solution of 3.0g 12M hydrochloric acid, be stirred at room temperature to
It is completely dissolved, then is added into system after 0.032mol aluminium isopropoxides, 40 DEG C of stirring 24h, gained settled solution is poured into culture
In ware, solvent flashing handles 24h at 60 DEG C;Then, gained solid is added to 20mL and contains 0.004mol cerous nitrates and 0.5g
In the ethanol solution of deionized water, in sealing autoclave at 100 DEG C after solvent heat grafting processing 24h, suction filtration is done
Dry, 450 DEG C of roasting 5h obtain cerium-aluminium composite oxide mesoporous material.
XRD characterization results show that prepared sample shows the two-dimentional hexagonal mesoporous pore passage structure of high-sequential.SEM-EDX
Characterization result further confirms that Al/Ce atomic ratios are 8.1: 1 in sample, and Al, Ce species can reach height on atomic level
It is dispersed.
N2 adsorption characterization result shows that the mesoporous pore size of gained cerium-aluminium composite oxide mesoporous material is 5.2nm, compares table
Area is 348m2/ g, pore volume is 0.45cm3/g.Sample is calcined 1h at 1000 DEG C, structural behaviour does not change.
0.1g ceriums-aluminium composite oxide mesoporous material, 10mL acetonitriles, 3mL hexamethylenes and 5mL TBHPs is taken to add
Enter in reactor, 4h is reacted at 80 DEG C.Cyclohexane selectivity catalytic oxidation Evaluation results show that resulting materials are 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 acids, add 40mL contain in the ethanol solution of 2.0g 2M sulfuric acid,
It is stirred at room temperature to being completely dissolved, then is added into system after 0.040mol isobutanol aluminums, 45 DEG C of stirring 24h, gained is clarified molten
Liquid is poured into culture dish, and solvent flashing handles 24h at 60 DEG C;Then, gained solid is added to 30mL and contains 0.003mol nitre
In the ethanol solution of sour nickel and 2g deionized water, the solvent heat grafting processing 24h at 120 DEG C in sealing autoclave
Afterwards, suction filtration, is dried, 550 DEG C of roasting 5h, obtains nickel-aluminum composite oxides mesoporous material.
XRD characterization results show that prepared sample shows the two-dimentional hexagonal mesoporous pore passage structure of high-sequential, and hole wall
Interior Ni, Al species reach that the high uniformity on atomic level disperses.Determined through SEM-EDX, Al/Ni atomic ratios are 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 is 0.47cm3/g.Sample is calcined 1h at 1000 DEG C, structural behaviour does not change.
0.5g is taken through H2Nickel-aluminum composite oxides mesoporous material after being activated at 600 DEG C, is filled in fixed-bed micro-reactor
Interior, it is 2 mixed gas to be passed through methane and oxygen molar ratio, in progress methane synthesis gas reaction, time 1h at 600 DEG C.Instead
Should result show that resulting materials are to the conversion ratio of methane up to 85.2%, and carbon monoxide yield is up to 89.6% in product.
Embodiment 6.
Take 4.2g EO27PO61EO27, 1.6g glacial acetic acid, add 40mL contain in the ethanol solution of 2.0g 6M hydrochloric acid,
It is stirred at room temperature to being completely dissolved, then is added into system after 0.038mol aluminum nitrates, 30 DEG C of stirring 24h, by gained settled solution
Pour into culture dish, solvent flashing handles 48h at 60 DEG C;Then, gained solid is added to 20mL and contains 0.003mol sulfuric acid
In manganese and the ethanol solution of 2g deionized waters, in sealing autoclave at 100 DEG C after solvent heat grafting processing 24h,
Suction filtration, is dried, 650 DEG C of roasting 5h, obtains manganese-aluminium composite oxide mesoporous material.
XRD characterization results show that prepared sample has two-dimentional hexagonal mesoporous pore passage structure, and SEM-EDX, which is characterized, to be confirmed, should
Mn, Al species reach that the high uniformity on atomic level disperses in material mesoporous wall, and wherein Al/Mn atomic ratios reach 12.8:
1。
N2 adsorption characterization result shows that gained manganese-aluminium composite oxide mesoporous material has homogeneous mesoporous pore size, average
Mesoporous pore size is 4.9nm, and specific surface area is 392m2/ g, pore volume is 0.44cm3/g.Sample is calcined 1h at 1000 DEG C, 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/
Min heating rate rises to 550 DEG C from room temperature, is passed through containing NO (0.25%)-CH4(0.28%)-O2(3%) He gas carries out CH4Urge
Change reduction NO reactions, reaction time 1h.Reaction result shows that under excess oxygen, resulting materials are to CH4With NO conversion ratio point
96.2% and 58.2% are not can reach.
Embodiment 7.
Take 7.2g EO106PO70EO106, 0.6g citric acids add 40mL and contain the ethanol solution of 2.6g 2M nitric acid
In, it is stirred at room temperature to being completely dissolved, then added into system after 0.042mol aluminum sulfate, 40 DEG C of stirring 24h, gained is clarified molten
Liquid is poured into culture dish, and solvent flashing handles 48h at 50 DEG C;Then, gained solid is added to 35mL and contains 0.005mol nitre
In the ethanol solution of sour copper and 0.8g deionized water, the solvent heat grafting processing 24h at 120 DEG C in sealing autoclave
Afterwards, suction filtration, is dried, 650 DEG C of roasting 5h, obtains copper-aluminium composite oxide mesoporous material.
XRD characterization results show that prepared sample shows the two-dimentional hexagonal mesoporous pore passage structure and height of high-sequential
One mesoporous pore size, and Cu species high uniformity can be scattered in aluminum oxide mesoporous wall on atomic level, Al/Cu atomic ratios
For 8.6: 1.
N2 adsorption characterization result shows that the mesoporous pore size of gained copper-aluminium composite oxide mesoporous material is 7.8nm, compares table
Area is 286m2/ g, pore volume is 0.55cm3/g.Sample is calcined 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/
Min heating rate 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
Reduce NO reactions, reaction time 1h.Reaction result shows that resulting materials are to C3H682.2% He is respectively reached with NO conversion ratio
56.3%。
Claims (10)
1. a kind of preparation method of bi-component composite alumina high heat stability ordered mesoporous material, methods described is as steps described below
Carry out:
1), according to silicon source: organic carboxyl acid: inorganic acid: absolute ethyl 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 absolute ethyl alcohol containing deionized water, adds silicon source, 20~60 DEG C are stirred
6~24h is mixed, settled solution is obtained;
2), by the settled solution under 30~60 DEG C of open states solvent flashing, obtain parcel surfactant and hole wall be rich
The alumina mesoporous material of the hydroxyl containing aluminium;
3), according to metal heteroatom presoma: absolute ethyl alcohol: deionized water=0.1~1: 10~100: 1~10 mole dispensing
Than metal heteroatom presoma is dissolved in the absolute ethyl 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 it is described parcel 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 handles 24~48h under the conditions of~150 DEG C, by product suction filtration and drying after processing;
5) the dried product, is calcined 2~5h at 300~800 DEG C, surfactant is removed, 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 described block copolymer nonionic surfactant is
It is EOnPOmEOn with structural formula, or EOnBOmEOn, using Pluronic F-127 as hydrophilic block, polycyclic oxypropylene or polycyclic
Oxygen butylene is used as the nonionic block copolymers of hydrophobic block, wherein n=10~180, m=5~100;EO represents oxireme,
PO represents propylene oxide, and BO represents butadiene monoxide.
3. preparation method according to claim 1, it is characterized in that described 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 described inorganic acid is hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid.
5. preparation method according to claim 1, it is characterized in that described 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 described metal heteroatom presoma be zirconium, cobalt, nickel,
Molybdenum, manganese, iron, chromium, copper, the soluble-salt of magnesium or cerium.
7. preparation method according to claim 6, it is characterized in that described 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
Stating material has the two-dimentional hexagonal mesoporous structure of high-sequential, 200~450m of specific surface area2/ g, 0.3~1.5cm of pore volume3/ g,
The mol 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 used as the application of catalyst.
10. bi-component composite alumina high heat stability ordered mesoporous material is used as acid catalyzed reaction, hydrocarbonization described in claim 8
The application of compound selective oxidation reaction, oxidative dehydrogenation or the anti-applications catalyst of hydrocarbon selective Reduction of NO.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109304154A (en) * | 2017-11-16 | 2019-02-05 | 中国石油化工股份有限公司 | A kind of order mesoporous TMCO- aluminium oxide catalyst and preparation method thereof that sulfur resistive is poisoned |
CN110280263A (en) * | 2019-06-26 | 2019-09-27 | 中国科学院山西煤炭化学研究所 | The alumina load manganese Raney nickel of removing flue gas nitrogen oxide and preparation and application |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102380362A (en) * | 2011-08-25 | 2012-03-21 | 太原理工大学 | Ordered zirconia-alumina mesoporous material and its preparation method |
CN103539173A (en) * | 2013-10-06 | 2014-01-29 | 太原理工大学 | Highly thermostable and ordered mesoporous alumina material and preparation method thereof |
WO2015126236A1 (en) * | 2014-02-18 | 2015-08-27 | Universidad Nacional Autónoma de México | Method for obtaining a composite aluminosilicate material containing alumina and nanozeolite |
CN105837033A (en) * | 2016-03-29 | 2016-08-10 | 中国工程物理研究院激光聚变研究中心 | Titanium-doped gel and preparation method thereof |
-
2017
- 2017-04-18 CN CN201710252681.4A patent/CN107115864B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102380362A (en) * | 2011-08-25 | 2012-03-21 | 太原理工大学 | Ordered zirconia-alumina mesoporous material and its preparation method |
CN103539173A (en) * | 2013-10-06 | 2014-01-29 | 太原理工大学 | Highly thermostable and ordered mesoporous alumina material and preparation method thereof |
WO2015126236A1 (en) * | 2014-02-18 | 2015-08-27 | Universidad Nacional Autónoma de México | Method for obtaining a composite aluminosilicate material containing alumina and nanozeolite |
CN105837033A (en) * | 2016-03-29 | 2016-08-10 | 中国工程物理研究院激光聚变研究中心 | Titanium-doped gel and preparation method thereof |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109304154A (en) * | 2017-11-16 | 2019-02-05 | 中国石油化工股份有限公司 | A kind of order mesoporous TMCO- aluminium oxide catalyst and preparation method thereof that sulfur resistive is poisoned |
CN109304154B (en) * | 2017-11-16 | 2021-11-05 | 中国石油化工股份有限公司 | Sulfur-poison-resistant ordered mesoporous TMCO-alumina catalyst and preparation method thereof |
CN110280263A (en) * | 2019-06-26 | 2019-09-27 | 中国科学院山西煤炭化学研究所 | The alumina load manganese Raney nickel of removing flue gas nitrogen oxide and preparation and application |
CN110357114A (en) * | 2019-08-14 | 2019-10-22 | 太原理工大学 | A kind of hole wall is rich in ordered meso-porous silicon oxide material and its preparation of microcellular structure |
CN110357114B (en) * | 2019-08-14 | 2022-08-16 | 太原理工大学 | Ordered mesoporous silicon oxide material with pore wall rich in microporous structure and preparation method thereof |
CN110773149A (en) * | 2019-09-23 | 2020-02-11 | 山西能源学院 | Preparation method of high-specific-surface-area aluminum-manganese SCR catalyst |
CN113522345A (en) * | 2021-07-22 | 2021-10-22 | 太原理工大学 | Ordered mesoporous Al-SBA-15 supported sulfated zirconia solid acid material and preparation and application thereof |
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