CN108212153A - A kind of manganese base composite oxidate catalyst of self-supporting modified with noble metals and its preparation method and application - Google Patents
A kind of manganese base composite oxidate catalyst of self-supporting modified with noble metals and its preparation method and application Download PDFInfo
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- CN108212153A CN108212153A CN201810115495.0A CN201810115495A CN108212153A CN 108212153 A CN108212153 A CN 108212153A CN 201810115495 A CN201810115495 A CN 201810115495A CN 108212153 A CN108212153 A CN 108212153A
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- China
- Prior art keywords
- catalyst
- base composite
- noble metals
- manganese base
- composite oxidate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 221
- 239000011572 manganese Substances 0.000 title claims abstract description 140
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 131
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000002131 composite material Substances 0.000 title claims abstract description 98
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title abstract description 21
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 49
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 16
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000011065 in-situ storage Methods 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 7
- 239000002585 base Substances 0.000 claims description 102
- 238000000034 method Methods 0.000 claims description 36
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 28
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000005470 impregnation Methods 0.000 claims description 21
- 239000000835 fiber Substances 0.000 claims description 20
- 239000012018 catalyst precursor Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 238000012545 processing Methods 0.000 claims description 15
- 229910052763 palladium Inorganic materials 0.000 claims description 14
- 229910052593 corundum Inorganic materials 0.000 claims description 13
- 238000007654 immersion Methods 0.000 claims description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 238000003421 catalytic decomposition reaction Methods 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- 239000010931 gold Substances 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 239000010948 rhodium Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- -1 pipe Substances 0.000 claims description 7
- 229910052703 rhodium Inorganic materials 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 16
- 238000000354 decomposition reaction Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000002474 experimental method Methods 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 20
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 239000003643 water by type Substances 0.000 description 16
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 11
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 5
- 229910016978 MnOx Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 3
- 150000002696 manganese Chemical class 0.000 description 3
- 235000002867 manganese chloride Nutrition 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- LRDAUUGUXQIHED-UHFFFAOYSA-N N.[N]=O Chemical compound N.[N]=O LRDAUUGUXQIHED-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical class O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
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- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical class O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical class O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 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 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical class [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- 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
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
- B01D53/8675—Ozone
-
- 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
- B01D53/90—Injecting reactants
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
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- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/30—
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- B01J35/393—
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- B01J35/50—
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- B01J35/58—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
Manganese base composite oxidate catalyst the invention discloses a kind of self-supporting modified with noble metals and its preparation method and application, the manganese base composite oxidate catalyst of the self-supporting modified with noble metals is one kind first growth in situ Al on aluminum substrate2O3Nanometer sheet forms catalyst carrier, then Supported Manganese base composite oxidate is obtained with active noble metals successively in the catalyst carrier；The manganese base composite oxidate is made of Mn oxide and auxiliary agent metal oxides, in the catalyst, mass percent shared by manganese base composite oxidate is 1~10%, and the mass percent shared by active noble metals is 0.001~0.1%, and surplus is catalyst carrier.Experiment shows：Catalyst thermal conductivity provided by the invention is good, permeability is high, stable structure, and with structurally ordered and pattern regularization feature, can fully meet the cartalytic decomposition effect of ozone and the catalytic performance requirement of the selective-catalytic-reduction denitrified reaction of ammonia.
Description
Technical field
The present invention is to be related to a kind of catalyst and its preparation method and application, is to be related to a kind of expensive gold of self-supporting specifically
Belong to modified manganese base composite oxidate catalyst and its preparation method and application, belong to catalysis technical field.
Background technology
In recent years, gaseous ozone (O3) generation technique had significant progress, be adapted to the ozone of various requirement
Generator is just constantly developed and is gone into operation.Chemical synthesis, health care, sewage disposal, food guarantor have extensively and profoundly been arrived in the application of ozone
Fresh, household electrical appliance etc. have made human lives and scientific technological advance important contribution.But ozone is also toxicity gas
Body, micro O3The symptoms such as (0.1~lppm) can make one to feel dizzy, eye is puckery, has sore throat.Low concentration ozone is to human body
Harm has caused the extensive concern of people, China《Indoor Air Quality standards (GB/TI8883-2002)》Provide lh mean concentrations
It must not exceed 0.16mg/m3, and at present people gradually increased by the probability that low concentration ozone expose, not only a large amount of NOx with wave
Atmospheric photochemistry pollution caused by hair property organic emission causes ozone concentration raising, indoors in environment, much
Office and household electrical appliance：Such as printer, duplicator, ozone air purifier also all discharge ozone, have been further exacerbated by interior
The deterioration of air regime, especially in air purification and water process the two industrial applications, if not carrying out ozone tail
Gas disposal works, and ozone concentration but will be severely exceeded.Therefore, the harm caused by ozone must cause the height weight of people
Depending on, producing ozoniferous place the decomposing, purifying of ozone is carried out in time, in order to avoid surrounding population is damaged.
About the research of ozone decomposed method, external such as Japan, the U.S., Germany are studied more at present, studies in China compared with
It is few.Current main ozone decomposed method has：Active carbon adsorption, thermal decomposition method, electromagenetic wave radiation decomposition method, medicament, which absorb, to be divided
Solution, atmospheric dilution exhaust method, catalytic decomposition etc., wherein, catalytic decomposition is with safety is preferable, economy is higher, place
Manage the advantages that effect is good, it is considered to be ideal ozone decomposed method.
Catalyst used in catalytic decomposition is mainly activated carbon (AC), transition metal oxide and noble metal etc..With work
Property charcoal as adsorption stuffing removing ozone method be usually used in industrial production, this method is although simple and convenient, but use when
Between a length, activated carbon easily loses activity, it is therefore desirable to often replace or regenerated carbon, and this method be only applicable to it is low dense
Spend ozone；In addition, this method is affected by factors such as humidity, air-flow, pressure and concentration, there is sizable limitation,
And explosive (Sichuan environment, 2001,20,1) at high concentrations.It oxide-based is urged for the transition element metal of ozone decomposed
The active component of agent mainly has the metal oxides such as manganese, cobalt, copper, iron, nickel and silver, and catalyst carrier mainly has γ-Al2O3、
TiO2、SiO2、ZrO2, molecular sieve, several composite parts of activated carbon or more, such as：Utilize γ-Al2O3As carrier, with oxygen
Change manganese as active component, using rare earth element as auxiliary agent, obtain rear-earth-doped MnO2γ-the Al of modification2O3Catalyst
(CN105289585A), the advantages of this method is that preparation process is simple, and catalyst is at low cost, and performance is stablized, ozone decomposed
Efficient, shortcoming is that catalyst anti humility performance obtained is poor；In another example：By the use of activated carbon as carrier, prepared via infusion process
Obtain using manganese oxide as active component, Co3O4The MnO of doping2-Co3O4Catalyst (Industrial Catalysis, 2002,10,6), 25
℃、0.1MPa、20000h-1、O3Concentration 200ppm, relative humidity>O after reaction 8h under 80% reaction condition3Conversion ratio is
78%, although catalyst anti humility performance has obtained certain raising, still there is certain gap with practical ozone decomposition catalyst.
Mainly there are gold, palladium, platinum, rhodium etc. for the noble metal of ozone decomposed, such as：By Pt of the content 0.0024%~0.47%,
0.038%~0.75% Pd loads to Al2O3Upper obtained catalyst, works as O3A concentration of 0.5mg/m3, air speed 5000h-1When,
822h, ozone decomposed rate are 100%；Pt, Re are loaded on activated carbon and diatomite, the ratio between Pt/Re is 2~10:1, work as O3
A concentration of 10mg/m3When, the ozone decomposed rate that catalyst for 24 hours is decomposed at 20 DEG C is 81%；Pt, Pd, Rh are loaded into Al2O3
On obtained catalyst, it is also quite preferable (Sichuan environment, 2001,20,1) to the catalytic decomposition effect of ozone；Pd, Mn are born
It is downloaded to SiO2-Al2O3On obtained Pd-MnOx/SiO2-Al2O3Catalyst (catalysis journal, 2009,30,1), at 45 DEG C and
510000h-1Under the conditions of carry out 95h life tests after, O3Conversion ratio be more than 90%, catalyst activity and water vapor performance are equal
Higher than the MnOx/SiO for being not added with Pd2-Al2O3Catalyst.Facts proved that there is noble metal catalyst higher ozone decomposed to live
Property, and the water vapor performance of catalyst of transition metal oxide is greatly improved, but higher cost again limits its big rule
Mould application.It is comprehensive apparently, the selection of the catalyst used in catalytic decomposition should based on the transition metal oxides such as Mn, Co, Ni,
It is aided with the noble metals such as Pd, Pt, Ru, Ce or rare earth metal.But the catalyst currently used for ozone decomposed is mostly metal oxidation
Object or metal composite oxide, although with certain service life, the later stage is using required coating or extrusion forming etc.
Operation so that preparation process is more complicated, is difficult to realize large-scale production；Also, the metal oxide of commercialization ozone decomposed at present
Class catalyst needs larger gas treatment amount, and (air speed of commercial catalyst should reach 100000-280000h-1), it is easy to cause
Higher pressure drop of column, and then the high requirement of comparison is proposed to reaction unit or even causes safety accident；In addition, in order to
Diffusion and external diffusion limitation in gas during elimination reaction, it is general at present using reduce catalyst granules grain size or (and) increase
Modes such as reaction gas flow velocity, however high pressure drop can be further resulted in, and then the problem of bring many energy consumptions and safety etc..Cause
This offer is a kind of simple for process, and ozone decomposed is efficient, and anti humility performance is excellent, is widely used, and service life is long, gas treatment amount
Greatly, the ozone catalyst suitable for the operation of high-throughput low pressure drop is of great significance.
In addition, energy resource structure of the China based on coal is difficult to change on short terms, in 30~50 following years
It will also continue to be maintained for up to 70% or so proportion, wherein coal-burning power plant is more than the 1/3 of the annual output of coal in China with coal.It is coal-fired
Contain various air pollutants in the flue gas of generation, such as dust, SO2, NOx (nitrogen oxides), wherein NOx meeting is discharged into air
It forms acid rain, photochemical fog or even destroys ozone layer.The discharge capacity of coal-burning power plant NOx accounts for the one of national NOx discharge at present
More than half.It is promulgated according in January, 2012 day《Thermal power plant's air pollution emission standard regulation (GB13223-2011)》, NOx is most
Height allows concentration of emission 200mg/m3, therefore, controlling the discharge of NOx has become coal-burning power plant after flue gas ash removal, desulfurization
Section 3 keypoint treatment works.
Current flue-gas denitration process is broadly divided into 3 class of dry method, semidry method and wet method at present, and wherein dry method includes selection
Property noncatalytic reduction (SNCR), selective catalytic reduction (SCR), electron beam combined desulfurization and denitration method；Semidry method is active
Charcoal combined desulfurization and denitration method；Wet method has ozone oxidation absorption process etc..In numerous denitration technologies, ammonia selective catalytic reduction
(NH3- SCR) technology because practicability, conversion ratio and selectivity it is higher the advantages that, it is considered to be one of most effective denitration technology.
The technological core of Selective Catalytic Reduction of NO x is SCR catalyst, directly affect SCR system denitration efficiency and operation into
This.Existing SCR catalyst can be divided into three categories according to the difference of ingredient：Noble metal catalyst, molecular sieve catalyst and metal
Oxide catalyst.Noble metal such as Pt, Rh, Pd catalyst is earliest SCR catalyst, is still in diesel engine denitration triple effect at present
The main component of catalyst, later vanadium series catalyst be introduced in SCR system, optimum activity temperature range many places are in 250
Between~400 DEG C, vanadium class/Ti-base catalyst comercial operation in coal-burning power plant's SCR system at present.Zeolite molecular sieve class SCR
The characteristics of active range of catalyst is high is mainly used for the higher operating mode of delivery temperature, the activity temperature of existing denitrating catalyst
Degree focuses mostly at 300~400 DEG C, in order to avoid the Repeat-heating of flue gas, by NH3- SCR reactors are placed in deduster, desulfurization
Before device, but this can make catalyst because of high concentration SO2And be poisoned, while by dust washed away and flying dust in impurity dirt
Dye；The effective way for solving the problems, such as this is after SCR reactors are placed in deduster, desulfurizer, researches and develops low temperature
(being less than 250 DEG C) NH3SCR denitration technology, and low temperature NH3The core of SCR denitration technology is the preparation of effective catalyst with grinding
Hair.In metal oxide catalyst, the oxide of transition metal such as Fe, Cr, Cu, Co, Mn are reacted SCR all with preferable low
Warm activity, the wherein low temperature active of MnOx is best, therefore manganese-based catalyst has obtained widest research.At present, manganese-based catalyst
Research focus mostly in support type low temperature NH3SCR catalyst, such catalyst is mainly by active component and carrier two parts group
Into, wherein, active component includes the oxide of Mn oxide and manganese and other metals composition, and carrier mainly has Al2O3(Mn-Ce/
γ-Al2O3, CN104874394A), TiO2(Mn-Co-Ce/TiO2, CN104289227A), activated carbon (MnOx/AC/C,
Catal, Today, 2007,126,406-411), cordierite (MnOx-CeO2-Nb2O5/ cordierite, Appl.Catal.B, 2009,
88,413-419) etc..Although Yi Shang support type manganese-based catalyst has preferable low temperature NH3- SCR performances, but on a large scale should
It uses and still suffers from that preparation process is more complicated, a series of problems, such as easily leading to high pressure drop in operating process.Therefore, it develops
A kind of cost is relatively low and with good low temperature activity, resistance to SO_2, the catalyst suitable for the operation of high-throughput low pressure drop and letter relatively
Single preparation method is just highly desirable.
A series of continuous development of voidages are high, mass-and heat-transfer performance is good metal and nonmetallic materials, to be used for ozone
Cartalytic decomposition effect and low temperature NH3The initiative of the efficient catalyst of-SCR reactions provides opportunity.Integrated catalyst
Have many advantages, such as that bed pressure drop is low, dismounting is convenient, be easy to make and process.In self-contained structure carrier area load active component system
Standby catalyst, active component particles size is small and uniform, has the excellent mass-and heat-transfer performance of self-contained structure carrier concurrently, meets catalysis
Efficient requirement is reacted, and requirement of the reaction process to high-throughput low pressure drop operation can be met.
In addition, in Chinese invention patent " a kind of integrated catalyst of CN201410168177 and its preparation method and application "
It discloses a kind of metal phase supported on carriers active noble metals of attached oxide of the anchor of porous or supported active noble metal and helps
The catalyst of agent metal oxide and its aflame application is catalyzed in methane and VOCs, although mentioning institute in the patent specification
The active noble metals stated include at least one of palladium, platinum, ruthenium, rhodium, iridium, gold, silver, and the auxiliary agent metal oxides are selected from alkali
At least one of metal, alkaline-earth metal, lanthanide rare metal, boron, aluminium, gallium, titanium, zirconium, silicon, Mn oxide, the metal
The material of phase carrier is any one in nickel, copper, aluminium, iron, copper-nickel alloy, brass, but in the patent Example and application examples simultaneously
The preparation of undisclosed manganese-based catalyst and catalytic performance, especially obtained porous oxide layer containing noble metal present unformed
Pattern, the combination of catalyst layer and metal phase carrier are insecure, it is clear that are difficult to obtain the manganese with good ozone decomposed performance
Base composite oxidate catalyst (can specifically refer to the comparative example 3 of the present invention and application examples 1).
In conclusion the cartalytic decomposition effect of ozone and low temperature NH3- SCR reactions are required for solving gas in reaction process
Treating capacity leads to greatly the problem of high pressure drop.Therefore, finding one kind has good strong adhesion energy, and it is good to have self-contained structure carrier concurrently
Mass and heat transfer performance well, high-throughput low pressure drop operate effective integration, for the cartalytic decomposition effect of ozone and low temperature NH3-
The structure catalyst of SCR reactions, is a research topic rich in challenge and actual application value.
Invention content
In view of the above-mentioned problems existing in the prior art, the object of the present invention is to provide a kind of manganese of self-supporting modified with noble metals
Base composite oxidate catalyst and preparation method thereof and its cartalytic decomposition effect and ammonia selective catalytic reduction in ozone take off
Application in nitre reaction.
For achieving the above object, the technical solution adopted by the present invention is as follows：
A kind of manganese base composite oxidate catalyst of self-supporting modified with noble metals is one kind first growth in situ on aluminum substrate
Al2O3Nanometer sheet forms catalyst carrier, then Supported Manganese base composite oxidate and the active noble metals successively in the catalyst carrier
It obtains；The manganese base composite oxidate is made of Mn oxide and auxiliary agent metal oxides, in the self-supporting noble metal
In modified manganese base composite oxidate catalyst, the mass percent shared by manganese base composite oxidate is 1~10%, your active gold
The mass percent for belonging to shared is 0.001~0.1%, and surplus is catalyst carrier.
Preferably, the material of the aluminum substrate is metallic aluminium or aluminium-containing alloy；The morphosis of the aluminum substrate
Any one in foam, fiber, fibrofelt, silk, silk screen, piece, foil, pipe, particle.
As further preferred scheme, the trepanning degree of the foam is 10~120PPI；A diameter of the 1 of the fiber~
150 microns；The fibrofelt is the entirety with three-dimensional porous structure formed by a diameter of 1~150 micron of fiber sintering
Formula fibrofelt；A diameter of 0.15~5.00 millimeter of the silk；The silk screen is by a diameter of 0.15~5.00 millimeter of silk thread
It weaves；The thickness of described is 0.1~2 millimeter；The thickness of the foil is 0.5~100 micron；The outer diameter of the pipe is 2
~50 millimeters, wall thickness be 0.5~5 millimeter；A diameter of 0.2~2 millimeter of the particle.
Preferably, the auxiliary agent metal oxides for alkaline-earth metal, lanthanide rare metal, iron, cobalt, nickel, copper,
The oxide of at least one of titanium, zinc, gallium, indium, tin, yttrium, zirconium, niobium metal.
Preferably, the active noble metals are at least one of palladium, platinum, ruthenium, rhodium, iridium, gold, silver.
Preferably, the molar ratio of manganese and promoter metal is 0.5~10.
A kind of method of manganese base composite oxidate catalyst for preparing self-supporting modified with noble metals of the present invention, including
Following specific steps：
A) the growth in situ Al on aluminum substrate2O3Catalyst carrier is made in nanometer sheet；
B) it is urged with the mixed aqueous solution of Mn oxide presoma and auxiliary agent metal oxides presoma is obtained to step a)
Agent carrier carries out incipient impregnation processing, then takes out, and dries, and immersion at the beginning of obtained product aqueous sodium carbonate is moistened, so
It dries afterwards, washs, dries again, manganese base composite oxidate catalyst precursor is made；
C) with the precursor water solution of active noble metals to manganese base composite oxidate catalyst precursor made from step b)
Incipient impregnation processing is carried out, is then taken out, is dried, then roast at 300~600 DEG C 0.5~5 hour to get described oneself
Support the manganese base composite oxidate catalyst of modified with noble metals.
Preferably, in step a), using hydro-thermal method on aluminum substrate growth in situ Al2O3Nanometer sheet.
Preferably, in step b), the Mn oxide presoma is in manganese nitrate, manganese chloride, manganese sulfate
At least one；The auxiliary agent metal oxides presoma refers to the nitrate containing promoter metal ion, sulfate, halogenation
Any one in object, oxalates, acetate, acetylacetonate.
As further preferred scheme, in step b), Mn oxide presoma and auxiliary agent metal oxides presoma it is mixed
In Heshui solution, the molar ratio of manganese and promoter metal is 0.5~10.
Preferably, in step b), the immersion at the beginning of the aqueous sodium carbonate that mass concentration is 0.5~7% is moistened.
Preferably, in step c), the presomas of active noble metals refers to water-soluble containing active noble metals
Nitrate (such as：Silver nitrate, palladium nitrate), sulfate, chloride (such as：Gold chloride, sodium chloraurate, ammonium chloraurate, ethylenediamine
Chlorauride, chloroplatinic acid, ruthenium trichloride, rhodium chloride, chloro-iridic acid), oxalates, acetate (such as：Palladium), acetylacetonate
In any one.
Preferably, in step c), active noble metals account for the 0.001~0.1% of catalyst gross mass.
Experiment shows：The manganese base composite oxidate catalyst of self-supporting modified with noble metals of the present invention both can be used as smelly
The catalyst of oxygen cartalytic decomposition effect, it is also possible to make the catalyst of the selective-catalytic-reduction denitrified reaction of ammonia.
Compared with prior art, the present invention has following conspicuousness advantageous effect：
The experimental results showed that：The manganese base composite oxidate catalyst of self-supporting modified with noble metals provided by the invention is in performance
It is upper to have many advantages, such as that stable structure, thermal conductivity are good, permeability is high, have on using and be easy to be molded, be easy to filling, be easily stored
The advantages that, and preparation method is simple, raw material is easy to get, structure-controllable, avoiding traditional manganese-based catalyst later stage application needs to apply
It covers or the problem of extrusion forming, can fully meet urging for catalytic decomposition of ozone reaction and the selective-catalytic-reduction denitrified reaction of ammonia
Change performance requirement；Especially, the manganese base composite oxidate catalyst of self-supporting modified with noble metals provided by the present invention shows
Structurally ordered and pattern regularization feature, catalyst layer is firmly combined with catalyst carrier, compared in CN201410168177
Unformed pattern integrated catalyst, there is more excellent catalytic decomposition of ozone performance, apply to ozone catalytic point
Solve ideal catalyst of reaction.
Description of the drawings
Fig. 1 be catalyst carrier prepared by embodiment 1 optics (on) and SEM photograph (in, under)；
Fig. 2 be embodiment 1 prepare self-supporting modified with noble metals manganese base composite oxidate catalyst optics (on) and
SEM photograph (in, under)；
Fig. 3 be catalyst carrier prepared by embodiment 3 optics (on) and SEM photograph (in, under)；
Fig. 4 be embodiment 3 prepare self-supporting modified with noble metals manganese base composite oxidate catalyst optics (on) and
SEM photograph (in, under)；
Fig. 5 be catalyst carrier prepared by embodiment 5 optics (on) and SEM photograph (in, under)；
Fig. 6 be embodiment 5 prepare self-supporting modified with noble metals manganese base composite oxidate catalyst optics (on) and
SEM photograph (in, under)；
Fig. 7 is the manganese base composite oxidate catalyst of self-supporting modified with noble metals prepared by embodiment 6 under different times mirrors
SEM photograph；
Fig. 8 be embodiment 7 prepare catalyst carrier optics (on) and prepare self-supporting modified with noble metals manganese base
Composite oxide catalysts optics (in) and SEM photograph (under)；
Fig. 9 a and Fig. 9 b are scanning electron microscope (SEM) photo of the comparative catalyst of the preparation of comparative example 3 under different times mirrors.
Specific embodiment
Technical solution of the present invention is described in further detail and completely with reference to embodiment, comparative example and application examples.
Embodiment 1
A) 2.0g aluminum fibers (a diameter of 80 μm, length be 1~10mm) are weighed, are given birth in situ on aluminum fiber using hydro-thermal method
Long Al2O3Catalyst carrier is made in nanometer sheet；
B) at room temperature, 0.073g ferric chloride hexahydrates and 0.32g, 50wt% manganese nitrate solution are dissolved in 3mL deionizations
In water, then catalyst carrier made from step a) is carried out etc. with the prepared mixed water solution containing manganese nitrate and iron chloride
Volume impregnation processing, then takes out, and dries, and immersion at the beginning of the aqueous sodium carbonate that obtained product mass concentration is 2% is moistened, so
It dries afterwards, washs, dries again, manganese base composite oxidate catalyst precursor is made；
C) at room temperature, 0.0024g silver nitrates are dissolved in 3mL deionized waters, then with prepared silver nitrate aqueous solution
Incipient impregnation processing is carried out to manganese base composite oxidate catalyst precursor made from step b), is then taken out, is dried, then
2 hours manganese base composite oxidate catalyst to get the self-supporting modified with noble metals are roasted at 400 DEG C.
Through Inductively coupled plasma atomic emission spectrometry it is found that the self-supporting noble metal prepared by the present embodiment changes
Property manganese base composite oxidate catalyst in, mass percent shared by active noble metals Ag (silver) is 0.069%, and manganese base is compound
Oxide (Fe2O3-MnO2) shared by mass percent for 5%, the molar ratio of manganese/iron is 3.1, remaining is catalyst carrier.
Fig. 1 be catalyst carrier manufactured in the present embodiment optics (on) and SEM photograph (in, under)；As seen from Figure 1, institute
The catalyst carrier of preparation shows the characteristics of structurally ordered and pattern regularization.
Fig. 2 be the manganese base composite oxidate catalyst of self-supporting modified with noble metals manufactured in the present embodiment optics (on) and
SEM photograph (in, under)；From Figure 2 it can be seen that the manganese base composite oxidate catalyst of prepared self-supporting modified with noble metals is also presented
The characteristics of going out structurally ordered and pattern regularization, and load catalyst layer (active noble metals and manganese base on a catalyst support
Composite oxides) without the phenomenon that peeling off unevenness of cracking, the catalyst layer and catalyst carrier that illustrate the catalyst are firmly combined with.
In addition, the present embodiment can also carry out following develop：
Aluminum metal in step a) can also be aluminium alloy (e.g., 2A01：AlCu2.5Mg0.5；5A02：A1Mg2.5；
7A09：AlZnMgCu1.5；ZAlMg5Si) fiber, remaining condition are constant；
The morphosis of aluminum metal in step a) can also be in foam, fibrofelt, silk, silk screen, piece, foil, pipe, particle
At least one, remaining condition is constant；
The mass concentration of aqueous sodium carbonate in step b) selects in 0.5~7%, remaining condition is constant；
Calcination temperature in step c) selects in 300~600 DEG C, remaining condition is constant；
Roasting time in step c) selected in 0.5~5 hour, remaining condition is constant.
Embodiment 2
A) with the step a) of embodiment 1；
B) at room temperature, 0.013g lanthanum nitrate hexahydrates and 0.03g Manganous sulfate monohydrates are dissolved in 3mL deionized waters,
Then catalyst carrier made from step a) is carried out in equal volume with the mixed water solution of prepared sulfur acid manganese and lanthanum nitrate
Impregnation then takes out, drying, and immersion at the beginning of the aqueous sodium carbonate that obtained product mass concentration is 2% is moistened, and is then dried
It does, washing, dry again, manganese base composite oxidate catalyst precursor is made；
C) at room temperature, 0.0013g six is hydrated chloroplatinic acid to be dissolved in 3mL deionized waters, then with prepared chloroplatinic acid
Aqueous solution carries out incipient impregnation processing to manganese base composite oxidate catalyst precursor made from step b), then takes out, and dries
It is dry, then 1 hour manganese base composite oxidate catalyst to get the self-supporting modified with noble metals is roasted at 600 DEG C.
Through Inductively coupled plasma atomic emission spectrometry it is found that the self-supporting noble metal prepared by the present embodiment changes
Property manganese base composite oxidate catalyst in, mass percent shared by active noble metals Pt (platinum) is 0.02%, and manganese base is compound
Oxide (La2O3-MnO2) shared by mass percent for 1%, the molar ratio of manganese/lanthanum is 5.6, remaining is catalyst carrier.
Embodiment 3
A) 8 a diameter of 36mm are weighed, (3g, a diameter of 0.3mm of aluminum fiber, thickness are about mesh number for the aluminium nets of 30 mesh
0.4mm), using hydro-thermal method in aluminium net growth in situ Al2O3Catalyst carrier is made in nanometer sheet；
B) at room temperature, 0.25g Nickelous nitrate hexahydrates and 0.29g Manganous sulfate monohydrates are dissolved in 2mL deionized waters, so
Catalyst carrier made from step a) is soaked in equal volume with the mixed water solution of prepared sulfur acid manganese and nickel nitrate afterwards
Stain processing, then takes out, and dries, and immersion at the beginning of the aqueous sodium carbonate that obtained product mass concentration is 2% is moistened, and is then dried
It does, washing, dry again, manganese base composite oxidate catalyst precursor is made；
C) at room temperature, 0.031g tetra- is hydrated gold chloride to be dissolved in 2mL deionized waters, then with prepared gold chloride water
Solution carries out incipient impregnation processing to manganese base composite oxidate catalyst precursor made from step b), then takes out, and dries,
4 hours manganese base composite oxidate catalyst to get the self-supporting modified with noble metals are roasted at 300 DEG C again.
Through Inductively coupled plasma atomic emission spectrometry it is found that the self-supporting noble metal prepared by the present embodiment changes
Property manganese base composite oxidate catalyst in, mass percent shared by active noble metals Au (gold) is 0.04%, and manganese base is compound
Oxide (NiO-MnO2) shared by mass percent for 7%, the molar ratio of manganese/nickel is 1.9, remaining is catalyst carrier.
Fig. 3 be catalyst carrier manufactured in the present embodiment optics (on) and SEM photograph (in, under)；As seen from Figure 3, institute
The catalyst carrier of preparation shows the characteristics of structurally ordered and pattern regularization.
Fig. 4 be the manganese base composite oxidate catalyst of self-supporting modified with noble metals manufactured in the present embodiment optics (on) and
SEM photograph (in, under)；From fig. 4, it can be seen that the manganese base composite oxidate catalyst of prepared self-supporting modified with noble metals is also presented
The characteristics of going out structurally ordered and pattern regularization, and load catalyst layer (active noble metals and manganese base on a catalyst support
Composite oxides) without the phenomenon that peeling off unevenness of cracking, the catalyst layer and catalyst carrier that illustrate the catalyst are firmly combined with.
Embodiment 4
A) with the step a) of embodiment 3；
B) at room temperature, 0.029g Salzburg vitriols and 0.12g manganese chlorides are dissolved in 2mL deionized waters, Ran Houyong
The mixed water solution of prepared chloride containing manganese and copper sulphate carries out at incipient impregnation catalyst carrier made from step a)
Reason, then takes out, and dries, and immersion at the beginning of the aqueous sodium carbonate that obtained product mass concentration is 2% is moistened, and is then dried, is washed
It washs, dry again, manganese base composite oxidate catalyst precursor is made；
C) at room temperature, 0.00014g ruthenium trichlorides are dissolved in 2mL deionized waters, then with prepared ruthenium trichloride water
Solution carries out incipient impregnation processing to manganese base composite oxidate catalyst precursor made from step b), then takes out, and dries,
2 hours manganese base composite oxidate catalyst to get the self-supporting modified with noble metals are roasted at 500 DEG C again.
Through Inductively coupled plasma atomic emission spectrometry it is found that the self-supporting noble metal prepared by the present embodiment changes
Property manganese base composite oxidate catalyst in, mass percent shared by active noble metals Ru (ruthenium) is 0.0016%, and manganese base is answered
Close oxide (CuO-MnO2) shared by mass percent for 3%, the molar ratio of manganese/copper is 7.6, remaining is catalyst carrier.
Embodiment 5
A) aluminum fiber mat (2g, a diameter of 60 μm of aluminum fiber, thickness is about 2mm) of 6 a diameter of 16mm is weighed, using water
Hot method growth in situ Al in aluminum fiber mat2O3Catalyst carrier is made in nanometer sheet；
B) at room temperature, 0.12g cabaltous nitrate hexahydrates and 0.36g, 50wt% manganese nitrate solution are dissolved in 2mL deionized waters
In, then catalyst carrier made from step a) is carried out with the prepared mixed water solution containing manganese nitrate and cobalt nitrate to wait bodies
Product impregnation, then takes out, and dries, and immersion at the beginning of the aqueous sodium carbonate that obtained product mass concentration is 2% is moistened, then
Drying, is dried at washing again, and manganese base composite oxidate catalyst precursor is made；
C) at room temperature, 0.012g palladium nitrates are dissolved in 2mL deionized waters, then with prepared palladium nitrate aqueous solution pair
Manganese base composite oxidate catalyst precursor made from step b) carries out incipient impregnation processing, then takes out, and dries, then
2 hours manganese base composite oxidate catalyst to get the self-supporting modified with noble metals are roasted at 500 DEG C.
Through Inductively coupled plasma atomic emission spectrometry it is found that the self-supporting noble metal prepared by the present embodiment changes
Property manganese base composite oxidate catalyst in, mass percent shared by active noble metals Pd (palladium) is 0.09%, and manganese base is compound
Oxide (Co2O3-MnO2) shared by mass percent for 6%, the molar ratio of manganese/cobalt is 2.2, remaining is catalyst carrier.
Fig. 5 be catalyst carrier manufactured in the present embodiment optics (on) and SEM photograph (in, under)；As seen from Figure 5, institute
The catalyst carrier of preparation shows the characteristics of structurally ordered and pattern regularization.
Fig. 6 be the manganese base composite oxidate catalyst of self-supporting modified with noble metals manufactured in the present embodiment optics (on) and
SEM photograph (in, under)；As seen from Figure 6, the manganese base composite oxidate catalyst of prepared self-supporting modified with noble metals is also presented
The characteristics of going out structurally ordered and pattern regularization, and load catalyst layer (active noble metals and manganese base on a catalyst support
Composite oxides) without the phenomenon that peeling off unevenness of cracking, the catalyst layer and catalyst carrier that illustrate the catalyst are firmly combined with.
In addition, the present embodiment can also carry out following develop：
Other conditions can be kept constant, make the expensive gold of self-supporting of preparation by regulating and controlling the dosage of palladium nitrate in step c)
Belong to the load capacity of Pd in the manganese base composite oxidate catalyst of modification in 0.001~1.0wt%.
Embodiment 6
A) with the step a) of embodiment 5；
B) at room temperature, 0.32g Magnesium dichloride hexahydrates and 0.56g, 50wt% manganese nitrate solution are dissolved in 2mL deionized waters
In, then catalyst carrier made from step a) is carried out with the prepared mixed water solution containing manganese nitrate and magnesium chloride to wait bodies
Product impregnation, then takes out, and dries, and immersion at the beginning of the aqueous sodium carbonate that obtained product mass concentration is 2% is moistened, then
Drying, is dried at washing again, and manganese base composite oxidate catalyst precursor is made；
C) at room temperature, 0.002g rhodium chlorides are dissolved in 2mL deionized waters, it is then water-soluble with prepared rhodium chloride
Liquid carries out incipient impregnation processing to manganese base composite oxidate catalyst precursor made from step b), then takes out, and dries, then
5 hours manganese base composite oxidate catalyst to get the self-supporting modified with noble metals are roasted at 400 DEG C.
Through Inductively coupled plasma atomic emission spectrometry it is found that the self-supporting noble metal prepared by the present embodiment changes
Property manganese base composite oxidate catalyst in, mass percent shared by active noble metals Rh (rhodium) is 0.03%, and manganese base is compound
Oxide (CuO-MnO2) shared by mass percent for 10%, the molar ratio of manganese/copper is 0.7, remaining is catalyst carrier.
Fig. 7 is the manganese base composite oxidate catalyst of self-supporting modified with noble metals manufactured in the present embodiment under different times mirrors
SEM photograph；As seen from Figure 7, the manganese base composite oxidate catalyst of prepared self-supporting modified with noble metals also shows knot
Structure is orderly and the characteristics of pattern regularization, and (active noble metals and manganese base are compound for the catalyst layer of load on a catalyst support
Oxide) without the phenomenon that peeling off unevenness of cracking, the catalyst layer and catalyst carrier that illustrate the catalyst are firmly combined with.
Embodiment 7
A) alumina particles (granularity 5mm) of 2.0g are weighed, using hydro-thermal method on alumina particles growth in situ Al2O3Nanometer sheet,
Catalyst carrier is made；
B) with the step b) of embodiment 5；
C) at room temperature, 0.005g palladiums are dissolved in 2mL deionized waters, then with prepared acetic acid aqueous palladium pair
Manganese base composite oxidate catalyst precursor made from step b) carries out incipient impregnation processing, then takes out, and dries, then
2 hours manganese base composite oxidate catalyst to get the self-supporting modified with noble metals are roasted at 500 DEG C.
Through Inductively coupled plasma atomic emission spectrometry it is found that the self-supporting noble metal prepared by the present embodiment changes
Property manganese base composite oxidate catalyst in, mass percent shared by active noble metals Pd (palladium) is 0.09%, and manganese base is compound
Oxide (Co2O3-MnO2) shared by mass percent for 6%, the molar ratio of manganese/cobalt is 2.3, remaining is catalyst carrier.
Fig. 8 be catalyst carrier manufactured in the present embodiment optics (on) and prepare self-supporting modified with noble metals manganese base
Composite oxide catalysts optics (in) and SEM photograph (under)；As seen from Figure 8, prepared catalyst carrier and self-supporting
The manganese base composite oxidate catalyst of modified with noble metals shows the characteristics of structurally ordered and pattern regularization, and is supported on and urges
Agent supported catalyst layer (active noble metals and manganese base composite oxidate) peels off the phenomenon that uneven without cracking, illustrates that this is urged
The catalyst layer of agent is firmly combined with catalyst carrier.
Embodiment 8
A) with the step a) of embodiment；
B) at room temperature, tetra- nitric hydrate indiums of 0.037g and 0.13g manganese chlorides are dissolved in 2mL deionized waters, Ran Houyong
The mixed water solution of prepared chloride containing manganese and indium nitrate carries out at incipient impregnation catalyst carrier made from step a)
Reason, then takes out, and dries, and immersion at the beginning of the aqueous sodium carbonate that obtained product mass concentration is 2% is moistened, and is then dried, is washed
It washs, dry again, manganese base composite oxidate catalyst precursor is made；
C) at room temperature, 0.003g six is hydrated chloro-iridic acid to be dissolved in 2mL deionized waters, then with prepared chloro-iridic acid water
Solution carries out incipient impregnation processing to manganese base composite oxidate catalyst precursor made from step b), then takes out, and dries,
2 hours manganese base composite oxidate catalyst to get the self-supporting modified with noble metals are roasted at 600 DEG C again.
Through Inductively coupled plasma atomic emission spectrometry it is found that the self-supporting noble metal prepared by the present embodiment changes
Property manganese base composite oxidate catalyst in, mass percent shared by active noble metals Ir (iridium) is 0.03%, and manganese base is compound
Oxide (In2O3-MnO2) shared by mass percent for 5%, the molar ratio of manganese/cobalt is 9.5, remaining is catalyst carrier.
Comparative example 1
A) aluminum fiber mat (2g, a diameter of 60 μm of aluminum fiber, thickness is about 2mm) of 6 a diameter of 16mm is weighed, using water
Hot method growth in situ Al in aluminum fiber mat2O3Catalyst carrier is made in nanometer sheet；
B) at room temperature, 0.12g cabaltous nitrate hexahydrates and 0.36g, 50wt% manganese nitrate solution are dissolved in 2mL deionized waters
In, then catalyst carrier made from step a) is carried out with the prepared mixed water solution containing manganese nitrate and cobalt nitrate to wait bodies
Product impregnation, then takes out, and dries, and immersion at the beginning of the aqueous sodium carbonate that obtained product mass concentration is 2% is moistened, then
Drying, is dried, then 2 hours self-supporting manganese base combined oxidations being modified to get non precious metal are roasted at 500 DEG C at washing again
Object catalyst.
Through Inductively coupled plasma atomic emission spectrometry it is found that in catalyst prepared by this comparative example, manganese base
Composite oxides (Co2O3-MnO2) shared by mass percent for 6%, the molar ratio of manganese/cobalt is 2.2, remaining is catalyst load
Body.
Comparative example 2
A) aluminum fiber mat (2g, a diameter of 60 μm of aluminum fiber, thickness is about 2mm) of 6 a diameter of 16mm is weighed, using water
Hot method growth in situ Al in aluminum fiber mat2O3Catalyst carrier is made in nanometer sheet；
B) at room temperature, 0.49g, 50wt% manganese nitrate solution are dissolved in 2mL deionized waters, then with prepared nitre
Sour manganese aqueous solution carries out incipient impregnation processing to catalyst carrier made from step a), then takes out, and dries, obtained product
The immersion at the beginning of the aqueous sodium carbonate that mass concentration is 2% is moistened, and is then dried, is washed, dries again, then roast 2 at 500 DEG C
The self-supporting manganese oxide catalyst that hour is modified to get non precious metal.
Through Inductively coupled plasma atomic emission spectrometry it is found that in catalyst prepared by this comparative example, manganese oxygen
Compound (MnO2) shared by mass percent for 6%, remaining is catalyst carrier.
Comparative example 3
With reference to the preparation method of embodiment 10 in patent of invention (CN201410168177), comparative catalyst is prepared.
A) 5 grams of sintering aluminum fiber (50 microns of fibre diameter) felts are weighed, are carried out with a concentration of 1% sodium hydrate aqueous solution
It takes out reactive aluminum 1 hour, after distilled water flushing, drying, roasts 2 hours in air, in 300 DEG C, the anchor for obtaining porous is attached
The metal phase carrier of oxide；
B) 5 grams of metal phase carrier made from step a) are weighed, with the palladium nitrate containing 0.001 gram of Pd, 0.125 gram of Co2O3Nitre
Sour cobalt and 0.125 gram of MnO2Manganese nitrate mixed aqueous solution, carry out incipient impregnation at room temperature, after drying, in air
2 hours are roasted in 500 DEG C to get the attached Al of anchor2O3Sintered aluminium fiber carrier on the integrated of supported palladium-cobalt oxide-manganese oxide urge
Agent.
It is learnt through plasma inductance linking atom emission spectrometry：In catalyst prepared by this comparative example, the matter of Pd
Amount content is 0.09%, Co2O3Mass content be 2.4%, MnO2Mass content be 2.3%.
Fig. 9 a and Fig. 9 b are scanning electron microscope (SEM) photo of the comparative catalyst of this comparative example preparation under different times mirrors；
By Fig. 9 a and Fig. 9 b as it can be seen that prepared comparative catalyst is in unformed pattern, and load catalyst on a catalyst support
Layer (active noble metals and manganese base composite oxidate) has the phenomenon that apparent cracking peeling and unevenness, illustrates the comparative catalyst's
The combination of catalyst layer and catalyst carrier is insecure.
Application examples 1
The catalyst progress catalytic decomposition of ozone performance test at room temperature of institute is prepared to Examples 1 to 8 and comparative example 1~3,
Specific test condition is as follows：It is evaluated using fixed bed reactors, reaction tube is quartz ampoule；Reaction raw materials are O3、O2And
The gaseous mixture of 90%Ar, O3A concentration of 1500 ± 45ppm (~3g/m3), total flow 1600mL/min, time 8h；O3By smelly
Oxygen Generator excitation generates, air source 10%O2/ Ar gaseous mixtures；Steam is blasted by Bubbling method, is controlled by the temperature for changing water
The steam amount of blasting, relative humidity (RH) are detected by hygrometer；The ozone concentration of reaction tube import and export by Ozone Monitor into
Row detection；The O that different catalysts change over time under different relative humidity at room temperature3Conversion ratio is shown in Table 1.
Under the different relative humidity of table 1 Examples 1 to 8 and comparative example 1~3 prepare catalyst to catalytic decomposition of ozone
The catalytic performance of reaction
From table 1：Existed using the manganese base composite oxidate catalyst of the self-supporting modified with noble metals prepared by the present invention
It still can efficiently decompose catalysis ozone, illustrate using prepared by the present invention under conditions of high throughput, high humility, high ozone concentration
The manganese base composite oxidate catalyst of self-supporting modified with noble metals has excellent catalytic decomposition of ozone performance, and the same terms
Under, catalytic performance is substantially better than self-supporting manganese base composite oxidate catalyst/comparative example that the non precious metal of comparative example 1 is modified
The self-supporting manganese oxide catalyst and the integrated catalyst of comparative example 3 that 2 non precious metal is modified.
Application examples 2
NO selective catalysis is carried out to the manganese base composite oxidate catalyst of self-supporting modified with noble metals prepared by embodiment 5
Reducing property is tested, and specific test condition is as follows：It is evaluated using fixed bed reactors, reaction tube is internal diameter 18mm quartz
Pipe；Reaction raw materials are NO, NH3、O2And N2Gaseous mixture, NO a concentration of 1000ppm, NH3A concentration of 1000ppm, 3%O2, N2
For Balance Air, total flow 200mL/min, air speed 6000mL/ (g h)；Catalyst amount is 2.0g, investigates temperature range 120
~300 DEG C；Reaction gas reacts at a set temperature after mixer, into fixed bed reactors, using diamond heating,
Digital temperature control instument temperature control；The monitoring of tail gas NO concentration is carried out using intelligent flue gas analyzer；In order to ensure the accuracy of data and
Reliability, each measurement condition at least stablize 50min；The NO conversion ratios of catalyst pair are shown in Table 2 under different temperatures.
The manganese base composite oxidate catalyst for nitrogen monoxide ammonia of self-supporting modified with noble metals prepared by 2 embodiment 5 of table
The catalytic performance of gas selective catalytic reduction reaction
| Reaction temperature (DEG C) | NO conversion ratios (%) |
| 120 | 89.2 |
| 150 | 98.7 |
| 180 | 97.6 |
| 210 | 93.2 |
| 240 | 84.5 |
| 270 | 81.9 |
| 300 | 80.5 |
From table 2：Existed using the manganese base composite oxidate catalyst of the self-supporting modified with noble metals prepared by the present invention
Still efficiently nitric oxide can be converted under high-throughput reaction condition by selective catalysis, illustrate that the self-supporting prepared by the present invention is expensive
Metal-modified manganese base composite oxidate catalyst for nitrogen monoxide ammonia selective catalytic reduction reaction has an excellent oxygen
Change nitrogen catalyzed conversion performance, can be used as the catalyst of the selective-catalytic-reduction denitrified reaction of ammonia.
Finally need indicated herein be：It the above is only the part preferred embodiment of the present invention, it is impossible to be interpreted as to this hair
The limitation of bright protection domain, those skilled in the art's the above according to the present invention make some it is nonessential improvement and
Adjustment all belongs to the scope of protection of the present invention.
Claims (10)
1. a kind of manganese base composite oxidate catalyst of self-supporting modified with noble metals, it is characterised in that：Be one kind on aluminum substrate
First growth in situ Al2O3Nanometer sheet formed catalyst carrier, then in the catalyst carrier successively Supported Manganese base composite oxidate with
Active noble metals obtain；The manganese base composite oxidate is made of Mn oxide and auxiliary agent metal oxides, it is described from
In the manganese base composite oxidate catalyst for supporting modified with noble metals, mass percent shared by manganese base composite oxidate for 1~
10%, the mass percent shared by active noble metals is 0.001~0.1%, and surplus is catalyst carrier.
2. the manganese base composite oxidate catalyst of self-supporting modified with noble metals according to claim 1, it is characterised in that：Institute
The material for stating aluminum substrate is metallic aluminium or aluminium-containing alloy；The morphosis of the aluminum substrate be selected from foam, fiber, fibrofelt, silk,
Any one in silk screen, piece, foil, pipe, particle.
3. the manganese base composite oxidate catalyst of self-supporting modified with noble metals according to claim 1, it is characterised in that：Institute
Auxiliary agent metal oxides are stated as in alkaline-earth metal, lanthanide rare metal, iron, cobalt, nickel, copper, titanium, zinc, gallium, indium, tin, yttrium, zirconium, niobium
At least one metal oxide.
4. the manganese base composite oxidate catalyst of self-supporting modified with noble metals according to claim 1, it is characterised in that：Institute
Active noble metals are stated as at least one of palladium, platinum, ruthenium, rhodium, iridium, gold, silver.
5. the manganese base composite oxidate catalyst of self-supporting modified with noble metals according to claim 1, it is characterised in that：Manganese
Molar ratio with promoter metal is 0.5~10.
6. a kind of method of manganese base composite oxidate catalyst for preparing self-supporting modified with noble metals described in claim 1,
It is characterized in that, comprises the following specific steps that：
A) the growth in situ Al on aluminum substrate2O3Catalyst carrier is made in nanometer sheet；
B) with the mixed aqueous solution of Mn oxide presoma and auxiliary agent metal oxides presoma to catalyst made from step a)
Carrier carries out incipient impregnation processing, then takes out, and dries, and immersion at the beginning of obtained product aqueous sodium carbonate is moistened, and is then dried
It does, washing, dry again, manganese base composite oxidate catalyst precursor is made；
C) manganese base composite oxidate catalyst precursor made from step b) is carried out with the precursor water solution of active noble metals
Incipient impregnation processing, then takes out, and dries, then roast 0.5~5 hour at 300~600 DEG C to get the self-supporting
The manganese base composite oxidate catalyst of modified with noble metals.
7. according to the method described in claim 6, it is characterized in that：In step a), given birth in situ on aluminum substrate using hydro-thermal method
Long Al2O3Nanometer sheet.
8. according to the method described in claim 6, it is characterized in that：In step b), with the carbonic acid that mass concentration is 0.5~7%
Sodium water solution just moisten by immersion.
9. a kind of application of the manganese base composite oxidate catalyst of self-supporting modified with noble metals described in claim 1, feature
It is：Catalyst as catalytic decomposition of ozone reaction.
10. a kind of application of the manganese base composite oxidate catalyst of self-supporting modified with noble metals described in claim 1, feature
It is：Catalyst as the selective-catalytic-reduction denitrified reaction of ammonia.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN111151306A (en) * | 2018-11-08 | 2020-05-15 | 中国科学院大连化学物理研究所 | Monolithic catalyst and preparation method and application thereof |
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| CN111229244B (en) * | 2018-11-28 | 2021-12-21 | 中蓝连海设计研究院有限公司 | Ozone catalytic oxidation catalyst and preparation method and application thereof |
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| CN114405546A (en) * | 2022-01-27 | 2022-04-29 | 郑州大学 | Manganese-loaded fiber catalyst for catalytic oxidation of ozone and preparation method and application thereof |
| CN114405546B (en) * | 2022-01-27 | 2023-06-23 | 郑州大学 | Manganese-loaded fiber catalyst for ozone catalytic oxidation and preparation method and application thereof |
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| CN115555018B (en) * | 2022-10-18 | 2024-02-20 | 华南理工大学 | Catalyst for low-temperature ozone catalytic oxidation of VOCs and preparation method thereof |
| CN115957759A (en) * | 2022-12-12 | 2023-04-14 | 河南农业大学 | Manganese-based synergistic monolithic catalyst and preparation method and application thereof |
| CN115957759B (en) * | 2022-12-12 | 2023-09-08 | 河南农业大学 | Manganese-based synergistic monolithic catalyst and preparation method and application thereof |
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