CN114471611A - Preparation method of noble metal and transition metal composite catalyst - Google Patents
Preparation method of noble metal and transition metal composite catalyst Download PDFInfo
- Publication number
- CN114471611A CN114471611A CN202210079884.9A CN202210079884A CN114471611A CN 114471611 A CN114471611 A CN 114471611A CN 202210079884 A CN202210079884 A CN 202210079884A CN 114471611 A CN114471611 A CN 114471611A
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- China
- Prior art keywords
- catalyst
- temperature
- transition metal
- noble metal
- roasting
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 49
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 42
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002905 metal composite material Substances 0.000 title claims description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 91
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 41
- 239000000446 fuel Substances 0.000 claims abstract description 38
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000001301 oxygen Substances 0.000 claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 31
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 22
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 22
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 6
- 150000002739 metals Chemical class 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 23
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 18
- 239000002828 fuel tank Substances 0.000 claims description 18
- 230000009467 reduction Effects 0.000 claims description 16
- 239000010955 niobium Substances 0.000 claims description 15
- 239000011572 manganese Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- XFHGGMBZPXFEOU-UHFFFAOYSA-I azanium;niobium(5+);oxalate Chemical compound [NH4+].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XFHGGMBZPXFEOU-UHFFFAOYSA-I 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 230000002829 reductive effect Effects 0.000 claims description 6
- 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 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 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 5
- 230000008030 elimination Effects 0.000 claims description 5
- 238000003379 elimination reaction Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 5
- 239000012716 precipitator Substances 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- XFVGXQSSXWIWIO-UHFFFAOYSA-N chloro hypochlorite;titanium Chemical compound [Ti].ClOCl XFVGXQSSXWIWIO-UHFFFAOYSA-N 0.000 claims description 4
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 4
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- XITGHTRVSNMXOD-UHFFFAOYSA-N [Nb].ClOCl Chemical compound [Nb].ClOCl XITGHTRVSNMXOD-UHFFFAOYSA-N 0.000 claims description 3
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 3
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- 235000006748 manganese carbonate Nutrition 0.000 claims description 3
- 229940093474 manganese carbonate Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 3
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 3
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000036284 oxygen consumption Effects 0.000 abstract description 8
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 39
- 239000000203 mixture Substances 0.000 description 25
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 16
- 229910001868 water Inorganic materials 0.000 description 16
- 239000007787 solid Substances 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- IPKFHTRHNBLGBR-UHFFFAOYSA-D azane niobium(5+) oxalate Chemical compound N.C(C(=O)[O-])(=O)[O-].[Nb+5].C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-].[Nb+5] IPKFHTRHNBLGBR-UHFFFAOYSA-D 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000009834 vaporization Methods 0.000 description 4
- 230000008016 vaporization Effects 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- -1 benzene aromatic hydrocarbon Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000010405 reoxidation reaction Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000012696 Pd precursors Substances 0.000 description 1
- 229910021069 Pd—Co Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910008933 Sn—Nb Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002737 fuel gas Substances 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
- 230000002779 inactivation Effects 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000520 microinjection Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
Classifications
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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
- B01J23/894—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 rare earths or actinides
-
- 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
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6484—Niobium
-
- 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
- B01J23/898—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 vanadium, tantalum, niobium or polonium
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- B01J35/56—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B64—AIRCRAFT; AVIATION; COSMONAUTICS
- B64D—EQUIPMENT FOR FITTING IN OR TO AIRCRAFT; FLIGHT SUITS; PARACHUTES; ARRANGEMENTS OR MOUNTING OF POWER PLANTS OR PROPULSION TRANSMISSIONS IN AIRCRAFT
- B64D37/00—Arrangements in connection with fuel supply for power plant
- B64D37/32—Safety measures not otherwise provided for, e.g. preventing explosive conditions
Abstract
The invention discloses a preparation method of a noble metal and transition metal catalyst. The catalyst mainly comprises a transition metal oxide carrier, and noble metals and transition metals loaded on the carrier, wherein the noble metals are at least one of Pt, Pd, Ru and Rh metals or oxides of the Pt, Pd, Ru and Rh metals, and the transition metals are at least one of Nb, Co, Mn, Zr, Cu and Ce oxides. The preparation process of the titanium dioxide loaded noble metal and transition metal catalyst is simple and does not generate secondary pollution, oxygen in fuel steam is eliminated efficiently at low temperature, and the catalyst has high catalytic activity and stability; the noble metal component has strong binding force with titanium dioxide, is not easy to fall off in the flying process of the airplane, and is particularly suitable for high-efficiency oxygen consumption of an airplane inerting system.
Description
Technical Field
The invention belongs to the technical field of airplane safety engineering, and particularly relates to a preparation method of a rare earth metal oxide-loaded noble metal and transition metal composite catalyst.
Background
The frequent occurrence of aviation accidents has caused aircraft manufacturers in countries around the world to continuously place higher demands on the safety of the aircraft. The establishment of an inerting system of an aircraft fuel tank is an important link for ensuring the safe flight of an aircraft. In recent years, many airlines in developed countries have developed studies on systems for inerting onboard fuel tanks. In 2010, the development of a green inert gas production system (GOBIGGS (TM)) was pioneered by Phyretechnologies Inc., of san Diego and it was demonstrated that this system could reduce the flammability of the fuel tank by substantially reducing the oxygen content, avoiding the potential explosion hazard due to ignition sources. The existing inert gas production system (OBIGGS) continuously discharges gasoline vapor into the environment, while the gobiggs (tm) system uses an advanced closed-loop catalytic inerting design, i.e. gasoline vapor is converted into inert gas and circulated in a closed-loop oil tank system, and pollutants such as hydrocarbon and the like cannot be discharged into the atmosphere, so that the damage of fuel vapor to the environment is reduced, and the danger to airport personnel is also reduced. In view of the current concerns about global warming and environmental and safety issues, the gobiggs (tm) system has become one of the important technologies for the development of large passenger aircraft and military aircraft.
The aviation industry in China is rapidly developed, the localization degree of aircraft manufacturing is increasingly improved, however, an onboard oil tank inerting system is not yet developed. In international research on the development of catalytic inerting systems for aircraft fuel tanks, the development of technologies for removing fuel gas and oxygen from the explosive limits by catalytic elimination has been mainly focused, and the main patent technologies include US7694916 (a technology development company of san diego), US5207734 (a french technology company), and US6463889 (a french technology company), the patents of which are registered in china. The key technology of these patents is the catalysts involved in the catalytic inerting system of the onboard fuel tank, including composite oxide catalysts, non-noble metal oxide catalysts, noble metal catalysts (platinum, palladium, gold, silver) and composite catalysts of noble and non-noble metals, rare earth catalysts, nitride and carbide catalysts, enzymes, and the like.
China Rp-3 aviation kerosene simulation can be expressed as C9.75H20.52I.e. with C as the main component9、C10、C 11. The temperature range of the environment of the onboard oil tank is-40-54 ℃, and the concentration of the balance gas organic matters (active components in steam) of the corresponding oil tank is 0.4-5% (volume percentage). Lowering of tank level due to fuel consumptionLow or varying air flows may introduce outside air and fuel vapor and oxygen concentrations in the fuel tank may be in the explosive range. For safety, the temperature of the catalytic inerting system of the aircraft fuel tank is set to 100-350 ℃ (CN101233049B), the mixed gas of air and fuel steam is introduced into a catalyst bed layer, the fuel steam and oxygen react under the action of the catalyst to generate carbon dioxide and water vapor, and the oxygen content is reduced, so that the fuel tank system is far away from the explosion limit. The water is filtered out by condensation, and the carbon dioxide is used as inert gas and returned to the oil tank to continuously participate in the deoxygenation cycle. In the low-temperature oxidation reaction of long paraffin and benzene aromatic hydrocarbon contained in Rp-3 aviation kerosene, carbon chain breakage and rearrangement are easy to generate polymerization and carbon formation on the surface of a catalyst, so that the carbonization and inactivation of the catalyst are caused. The key for solving the problem of low-temperature carbon formation of the catalyst in the inerting system of the airborne fuel tank is to improve the low-temperature alkane oxidation performance of the catalyst, namely directly oxidizing active components in fuel steam to CO/CO2。
The existing catalytic oxidation technology for organic active components in Rp-3 aviation kerosene has various technical defects, such as high catalytic oxidation ignition temperature, poor stability of a catalyst in resistance to carbon deposition and the like, and the technical requirements of a catalytic inerting system of an airborne fuel tank cannot be met.
Disclosure of Invention
The purpose of the invention is: provides a titanium dioxide loaded noble metal and transition metal catalyst and a preparation method thereof, and solves the problem that the technical requirement of an airborne fuel tank catalytic inerting system cannot be met.
The invention provides a preparation method of a noble metal and transition metal composite catalyst, which comprises the following steps:
1) dispersing a titanium precursor in ethanol, adding an alkaline precipitator to control the pH value of a titanium precursor solution to be 11-12, carrying out crystallization treatment for 4-8h at the temperature of 110-150 ℃, filtering, drying at the temperature of 80-150 ℃, and roasting at the temperature of 400-600 ℃ to obtain honeycomb-shaped titanium dioxide;
2) adding the titanium dioxide into a mixed solution containing a noble metal precursor and a transition metal precursor, adding a reduction precipitator, carrying out co-precipitation of the noble metal precursor and the transition metal precursor on the surface of the titanium dioxide by a reduction precipitation method, drying, roasting, introducing a reduction gas for reduction roasting, and introducing an oxidation gas for oxidation roasting to obtain the titanium dioxide-loaded noble metal and transition metal composite catalyst.
Further, the reduction precipitant is at least one selected from hydrogen peroxide, sodium borohydride and hydrazine hydrate.
Further, the noble metal is at least one selected from the group consisting of Pt, Pd, Ru, Rh metal or oxide, and the noble metal loading is 0 to 5 wt% and is not 0, based on the weight of the catalyst;
the transition metal is at least one of Nb, Co, Mn, Zr, Cu and Ce oxides, and the loading amount of the transition metal is 0-5 wt% and is not 0 based on the weight of the catalyst.
Further, the noble metal loading is from 0.5 to 3 weight percent, based on the weight of the catalyst.
Further, the transition metal loading is from 0.5 to 3 weight percent, based on the weight of the catalyst.
Further, the temperature range of the drying is 100-120 ℃; the drying atmosphere is air; the roasting temperature range is 400-600 ℃; the roasting atmosphere is air or nitrogen; the temperature range of the reduction roasting is 300-500 ℃; the reducing gas is N2 containing 1-20% by volume of H2; the temperature range of the oxidizing roasting is 300-500 ℃; the oxidizing gas was N2 containing 1-50 vol% O2.
Further, the precursor of titanium is selected from at least one of isopropyl titanate, titanium oxychloride, titanium tetrachloride and titanium sulfate.
Further, the noble metal precursor is selected from at least one of chloroplatinic acid, ammonium platinate, palladium chloride, palladium nitrate, ruthenium chloride and ruthenium acetate.
Further, the transition metal precursor is selected from at least one of ammonium niobium oxalate, niobium pentachloride, niobium oxychloride, cobalt nitrate, cobalt carbonate, cobalt sulfate, manganese nitrate, manganese carbonate, manganese sulfate, zirconium oxychloride, zirconium nitrate, copper sulfate, copper nitrate, cerium nitrate and cerium acetate.
Further, a low-temperature catalytic oxygen elimination method, which is used for eliminating oxygen by using the noble metal and transition metal composite catalyst prepared by the preparation method of any one of claims 1 to 9 in a green inerting system of an aircraft fuel tank; in the inerting system, the fuel vapor is Rp-3 fuel vapor with CH concentration of 10000-; the concentration of oxygen is 1-20% by volume; the reaction temperature is 115-140 ℃; the gas linear velocity of the catalyst bed is 0.4-14 m/s.
The invention has the advantages that:
the titanium dioxide loaded noble metal and transition metal composite catalyst prepared by the invention can be used for green inerting of a mobile oil tank, particularly for a green inerting system of an airborne oil tank, and can be used for efficient and safe low-temperature oxygen elimination.
The powder of the titanium dioxide loaded noble metal and transition metal composite catalyst is coated on a metal honeycomb carrier, and the performance test of the oxygen consumption reaction of a simulated airborne fuel tank with different Rp-3 fuel steam concentrations is carried out in a fixed bed reactor. At the catalyst bed temperature of 120-160 ℃, Rp-3 fuel steam can be completely converted into CO2And H2O; water vapor and CO at different concentrations2In the presence of titanium dioxide, the titanium dioxide supported noble metal and transition metal composite catalyst still maintains the above-mentioned excellent performance. The catalyst has high oxidation activity and high oxygen consumption efficiency on fuel components such as alkane, cyclane and aromatic hydrocarbon in Rp-3 fuel steam; in the stability test of repeated cyclic application, the stable oxygen consumption efficiency can be kept.
The titanium dioxide loaded noble metal and transition metal composite catalyst has simple preparation process and does not generate secondary pollution; the titanium dioxide carrier is easy to prepare silica sol and alumina sol, is coated on a metal honeycomb material with strong force and is not easy to fall off, and is suitable for an aircraft fuel tank green inerting system with large vibration.
Drawings
FIG. 1 is a graph of residual oxygen concentration over time after reaction over the catalyst of example 10 at an Rp-3 fuel vapor CH concentration of 40000ppm by volume, with an initial oxygen concentration of 10% by volume, and at 180 ℃;
FIG. 2 is a graph of residual oxygen concentration over time for the reaction on the catalyst of example 10 after 20 cycles at a fuel vapor CH concentration of Rp-3 of 40000pppm (by volume).
Detailed Description
According to one aspect of the present invention, there is provided a titanium dioxide-supported noble metal and transition metal composite catalyst for use in green inerting systems for aircraft fuel tanks. Under the action of the catalyst, the oxygen in the oil tank can be efficiently converted into carbon dioxide and water through catalytic oxidation. The catalyst disclosed by the invention is low in ignition temperature, good in sulfur poisoning resistance and carbon deposition resistance, very suitable for green inerting of an aircraft fuel tank, and good in application prospect.
The invention adopts titanium dioxide material prepared by a hydrothermal method as a carrier, uses a reduction precipitation method to load noble metal and transition metal precursor aqueous solution or alcohol solution, and obtains the titanium dioxide loaded noble metal and transition metal composite catalyst by drying, roasting, reducing and roasting.
The titanium dioxide carrier and the precursor of titanium can be one of isopropyl titanate, titanium oxychloride, titanium tetrachloride and titanium sulfate;
the preparation method of the titanium dioxide carrier is a hydrothermal synthesis method, and comprises the steps of adopting an alkaline precipitator such as urea, ammonia water, NaOH aqueous solution and the like to control the pH value of the cerium salt aqueous solution to be 11-12, carrying out crystallization treatment for 4-8h at the temperature of 110-150 ℃, filtering, drying (80-150 ℃), roasting (400-600 ℃), and obtaining honeycomb titanium oxide;
the noble metal is selected from one or more of Pt, Pd, Ru and Rh metal or oxide, more preferably the combination of two or more of Pt, Pd, Ru and Rh metal or oxide, and the content is 0-5 wt%, preferably 0.5-3 wt% based on the weight of the metal;
the Pt precursor of the noble metal is selected from chloroplatinic acid and ammonium platinate; the Pd precursor is selected from palladium chloride and palladium nitrate; the Ru precursor is selected from ruthenium chloride and ruthenium acetate;
the transition metal is one or more oxides of Nb, Co, Mn, Zr, Cu and Ce, preferably a combination of two or more oxides of Nb, Co, Mn, Zr, Cu and Ce, and the content of the transition metal is 0-5 wt%, preferably 0.5-3 wt% based on the weight of the metal;
the Nb precursor of the transition metal is selected from one of ammonium niobium oxalate, niobium pentachloride and niobium oxychloride; the precursor of Co is selected from one of cobalt nitrate, cobalt carbonate and cobalt sulfate; the manganese precursor is selected from one of manganese nitrate, manganese carbonate and manganese sulfate; the precursor of Zr is selected from one of zirconium oxychloride and zirconium nitrate; the precursor of Cu is selected from one of copper sulfate and copper nitrate; the precursor of Ce is selected from one of cerium nitrate and cerium acetate.
The titanium dioxide loaded noble metal and transition metal composite catalyst is dried and roasted in the preparation process, wherein the drying temperature is 80-150 ℃, and more preferably 100-120 ℃; the drying atmosphere is air; the roasting temperature is 400-600 ℃, and more preferably 400-500 ℃; the roasting atmosphere can be air or nitrogen, and is better air;
the titanium dioxide loaded noble metal and transition metal composite catalyst is subjected to reduction and reoxidation treatment in the preparation process, wherein the reduction temperature is 300-500 ℃, and is better at 400 ℃; the reducing gas may be 1% -20% H2/N2More preferably 1% to 5% H2/N2(ii) a The reoxidation temperature may be 300 ℃ to 500 ℃, preferably 400 ℃; the oxidizing gas may be 1% -50% O2/N2More preferably 10% to 25% O2/N2。
Example 1
2g of titanium oxychloride was dissolved in 40mL of ethanol, 3g of urea was added, and the mixture was placed in a 50mL stainless steel reaction vessel with a Teflon substrate and treated at 140 ℃ for 5 hours. After cooling to room temperature, filtering, washing the precipitate with deionized water, and drying the precipitate at 110 ℃ for 10 h; and finally, transferring the precipitate to a muffle furnace for roasting, wherein the initial temperature is 50 ℃, the temperature is raised to 450 ℃ at the temperature rise rate of 2 ℃/min, and the temperature is kept for 4h, so that the titanium dioxide carrier material is obtained.
0.5mL of palladium chloride and cobalt nitrate aqueous solution (Pd concentration is 20g/L, cobalt nitrate concentration is124g/L) was poured into a container containing 2g of the above-prepared titanium dioxide carrier, 10ml of deionized water was added, stirred for 2 hours, and 10ml of H was added dropwise2O2(30% water solution), stirring for 20min in a constant temperature water bath at 70 ℃, filtering, washing for several times by deionized water, drying overnight at 110 ℃, then putting into a muffle furnace, heating from 50 ℃ to 450 ℃ at the heating rate of 2 ℃/min in the air atmosphere, and preserving heat for 4 h. The resulting solid was cooled to 250 ℃ at 5% H2/N2Reducing for 3h in atmosphere; switching air atmosphere, heating to 450 ℃, and preserving heat for 4h to obtain Pd-Co/CeO2Catalyst, wherein the Pd content is 0.5 wt.% and the Co content is 1 wt.%.
Example 2
10g isopropyl titanate was dissolved in 40mL ethanol, 3g urea was added, and the mixture was placed in a 50mL Teflon-lined stainless steel reaction kettle and treated at 140 ℃ for 5 h. After cooling to room temperature, filtering, washing the precipitate with deionized water, and drying the precipitate at 110 ℃ for 10 hours; and finally, transferring the precipitate to a muffle furnace for roasting, wherein the initial temperature is 50 ℃, the temperature is raised to 450 ℃ at the heating rate of 2 ℃/min, and the temperature is kept for 4 hours to obtain the titanium dioxide carrier material.
1mL of ruthenium chloride and manganese nitrate aqueous solution (the concentration of Ru is 20g/L, and the concentration of manganese nitrate is 130g/L) is measured and poured into a container filled with 2g of the prepared titanium dioxide carrier, 10mL of deionized water is added, the mixture is stirred for 2 hours, 10mL of hydrazine hydrate solution is dropwise added, the mixture is placed in a constant-temperature water bath kettle at 70 ℃ and stirred for 20 minutes, the filtration is carried out, the deionized water is washed for a plurality of times, the mixture is dried at 110 ℃ overnight, the mixture is placed in a muffle furnace, the temperature is increased from 50 ℃ to 450 ℃ at the temperature increasing rate of 2 ℃/min in the air atmosphere, and the temperature is maintained for 4 hours. The resulting solid was cooled to 300 ℃ at 5% H2/N2Reducing for 3h in atmosphere; switching air atmosphere, heating to 450 ℃, and keeping the temperature for 4h to obtain Ru-Mn/TiO2Catalyst with a Ru content of 1 wt% and a Mn content of 2 wt%.
Example 3
10g of titanium sulfate was dissolved in 40mL of deionized water, 3g of urea was added, and the mixture was placed in a 50mL stainless steel reaction vessel with a Teflon substrate and treated at 140 ℃ for 5 hours. After cooling to room temperature, filtering, washing the precipitate with deionized water, and drying the precipitate at 110 ℃ for 10 h; and finally, transferring the precipitate to a muffle furnace for roasting, wherein the initial temperature is 50 ℃, the temperature is raised to 450 ℃ at the temperature rise rate of 2 ℃/min, and the temperature is kept for 4h, so that the titanium dioxide carrier material is obtained.
1mL of ruthenium chloride, palladium chloride and manganese nitrate aqueous solution (the concentration of Ru and Pd is 20g/L, and the concentration of manganese nitrate is 65g/L) is measured and poured into a container filled with 2g of the prepared titanium dioxide carrier, 10mL of deionized water is added, stirring is carried out for 2h, 1g of sodium borohydride is added, the mixture is placed in a constant-temperature water bath kettle at 70 ℃ and stirred for 20min, suction filtration is carried out, deionized water is washed for a plurality of times, drying is carried out at 110 ℃ overnight, then the mixture is placed in a muffle furnace, the temperature is increased from 50 ℃ to 450 ℃ at the temperature increasing rate of 2 ℃/min in the air atmosphere, and heat preservation is carried out for 4 h. The resulting solid was cooled to 320 ℃ at 5% H2/N2Reducing for 3h in atmosphere; switching air atmosphere, heating to 450 ℃, and preserving heat for 4h to obtain Ru-Pd-Mn/TiO2The catalyst had a content of both Ru and Pd of 1 wt% and a content of Mn of 1 wt%.
Example 4
1mL of chloroplatinic acid, palladium chloride and manganese nitrate aqueous solution (the concentration of Pt and Pd is 20g/L, and the concentration of manganese nitrate is 65g/L) are measured and poured into a container filled with 2g of the titanium dioxide carrier prepared in the example 1, 10mL of deionized water is added, stirring is carried out for 2h, 1g of sodium borohydride is added, the mixture is placed in a constant-temperature water bath kettle at 70 ℃ and stirred for 20min, suction filtration is carried out, deionized water is washed for a plurality of times, drying is carried out at 110 ℃ overnight, the mixture is placed in a muffle furnace, the temperature is increased from 50 ℃ to 450 ℃ at the temperature increasing rate of 2 ℃/min in the air atmosphere, and heat preservation is carried out for 4 h. The resulting solid was cooled to 300 ℃ at 5% H2/N2Reducing for 3h in atmosphere; switching air atmosphere, heating to 450 ℃, and preserving heat for 4h to obtain Pt-Pd-Mn/CeO2Catalyst, wherein the Pt and Pd contents are both 1 wt% and the Mn content is 1 wt%.
Example 5
1mL of chloroplatinic acid, palladium chloride and niobium oxalate ammonia water solution (the concentration of Pt and Pd are both 20g/L, the concentration of niobium oxalate ammonia is 200g/L) is measured and poured into a container filled with 2g of the titanium dioxide carrier prepared in the example 1, 10mL of deionized water is added, stirring is carried out for 2 hours, 10mL of hydrazine hydrate solution is dropwise added, the mixture is placed in a constant-temperature water bath kettle at 70 ℃ and stirred for 20min, suction filtration is carried out, deionized water is washed for several times, and the mixture is placed in a container 1Drying at 10 deg.C overnight, placing into muffle furnace, heating from 50 deg.C to 450 deg.C at 2 deg.C/min in air atmosphere, and maintaining for 4 h. The resulting solid was cooled to 250 ℃ at 5% H2/N2Reducing for 3h in atmosphere; switching air atmosphere, heating to 450 ℃, and preserving heat for 4h to obtain Pt-Pd-Ce/TiO2The catalyst had a Pt and Pd content of 1 wt% and a Ce content of 1 wt%.
Example 6
1mL of ruthenium chloride, chloroplatinic acid, palladium chloride and niobium oxalate ammonia solution (the concentration of Ru, Pt and Pd is 20g/L and the concentration of niobium oxalate ammonia is 200g/L) is weighed and poured into a container filled with 2g of the titanium dioxide carrier prepared in the example 1, 10mL of deionized water is added, the mixture is stirred for 2 hours, 10mL of hydrazine hydrate solution is dropwise added, the mixture is placed in a constant-temperature water bath kettle at 70 ℃ and stirred for 20 minutes, the filtration is carried out, the deionized water is washed for a plurality of times, the mixture is dried at 110 ℃ overnight and then placed into a muffle furnace, the temperature is raised from 50 ℃ to 450 ℃ at the temperature raising rate of 2 ℃/min in the air atmosphere, and the temperature is kept for 4 hours. The resulting solid was cooled to 250 ℃ at 5% H2/N2Reducing for 3h in atmosphere; switching air atmosphere, heating to 450 ℃, and preserving heat for 4h to obtain Ru-Pt-Pd-Nb/TiO2The catalyst contains 1 wt% of Ru, Pt and Pd and 1 wt% of Nb.
Example 7
1mL of ruthenium chloride, chloroplatinic acid, zirconium oxychloride and niobium oxalate ammonia aqueous solution (the concentrations of Ru and Pt are both 20g/L, and the concentrations of zirconium oxychloride and niobium oxalate ammonia are 71g/L and 100g/L respectively) are weighed and poured into a container filled with 2g of the titanium dioxide carrier prepared in the embodiment 1, 10mL of deionized water is added, the mixture is stirred for 2 hours, 10mL of hydrazine hydrate solution is added dropwise, the mixture is placed in a 70 ℃ constant-temperature water bath and stirred for 20 minutes, filtered, washed for several times by deionized water, dried overnight at 110 ℃, and heated from 50 ℃ to 450 ℃ at a heating rate of 2 ℃/min in an air atmosphere, and the temperature is kept for 4 hours. The resulting solid was cooled to 250 ℃ at 5% H2/N2Reducing for 3h in atmosphere; switching air atmosphere, heating to 450 ℃, and preserving heat for 4h to obtain Ru-Pt-Zr-Nb/TiO2The catalyst had a Ru and Pt content of 1 wt% and Zr and Nb contents of 2 wt% and 1 wt%, respectively.
Example 8
1mL of palladium chloride, chloroplatinic acid, copper nitrate, ammonium niobium oxalate and citric acid aqueous solution (the concentrations of Pd and Pt are both 20g/L, the concentrations of copper nitrate and ammonium niobium oxalate are respectively 59g/L and 100g/L) are measured and poured into a container filled with 2g of the titanium dioxide carrier prepared in the embodiment 1, 10mL of hydrazine hydrate solution is dropwise added, the mixture is placed in a constant-temperature water bath kettle at 70 ℃ and stirred for 20min, the mixture is subjected to suction filtration and deionized water washing for several times, dried at 110 ℃ overnight, then placed in a muffle furnace, heated from 50 ℃ to 450 ℃ at the heating rate of 2 ℃/min in the air atmosphere, and then the temperature is kept for 4 h. The resulting solid was cooled to 250 ℃ at 5% H2/N2Reducing for 3h in atmosphere; switching air atmosphere, heating to 450 ℃, and preserving heat for 4h to obtain Pd-Pt-Cu-Nb/TiO2The catalyst had a Pd and Pt content of 1 wt% and a Cu and Nb content of 2 wt% and 1 wt%, respectively.
Example 9
1mL of palladium chloride, chloroplatinic acid, aluminum nitrate and niobium ammonium oxalate solution (the concentrations of Pd and Pt are both 20g/L, and the concentrations of aluminum nitrate and niobium ammonium oxalate are respectively 158g/L and 100g/L) are measured and poured into a container filled with 2g of the titanium dioxide carrier prepared in the example 1, 1g of sodium borohydride is added, the mixture is placed in a constant-temperature water bath kettle at 70 ℃ and stirred for 20min, the suction filtration and the deionized water washing are carried out for a plurality of times, the mixture is dried at 110 ℃ overnight and then placed into a muffle furnace, the temperature is increased from 50 ℃ to 450 ℃ at the temperature increasing rate of 2 ℃/min in the air atmosphere, and the temperature is kept for 4 h. The resulting solid was cooled to 250 ℃ at 5% H2/N2Reducing for 3h in atmosphere; switching air atmosphere, heating to 450 ℃, and preserving heat for 4h to obtain Pd-Pt-Al-Nb/TiO2The catalyst has a Pd and Pt content of 1 wt% and Al and Nb contents of 2 wt% and 1 wt%, respectively.
Example 10
1mL of ruthenium chloride, palladium chloride, chloroplatinic acid, aluminum nitrate and niobium oxalate ammonia solution (the concentration of Ru, Pd and Pt is 20g/L, the concentration of stannous sulfate and the concentration of niobium oxalate ammonia are 158g/L and 100g/L respectively) are weighed and poured into a container filled with 2g of the titanium dioxide carrier prepared in the embodiment 1, 10mL of hydrazine hydrate solution is dropwise added, the mixture is placed into a constant-temperature water bath kettle at 70 ℃ to be stirred for 20min, the filtration is carried out, deionized water is washed for a plurality of times, the mixture is dried at 110 ℃ overnight and then is placed into a muffle furnace, and the temperature is raised at the speed of 2 ℃/min in the air atmosphereThe temperature is raised from 50 ℃ to 450 ℃ and the temperature is kept for 4 h. The resulting solid was cooled to 250 ℃ at 5% H2/N2Reducing for 3h in atmosphere; switching air atmosphere, heating to 450 ℃, and preserving heat for 4h to obtain Ru-Pd-Pt-Sn-Nb/TiO2The catalyst contains 1 wt% of Ru, Pd and Pt and 2 wt% and 1 wt% of Sn and Nb, respectively. The obtained catalyst reacts under the conditions that the concentration of Rp-3 fuel steam CH is 40000ppm (volume), the initial concentration of oxygen is controlled at 10 volume percent and the temperature is 180 ℃, and the change of the residual oxygen concentration along with time after the reaction is shown in figure 1; the resulting catalyst has a residual oxygen concentration over time as shown in FIG. 2 after 20 cycles at a fuel vapor CH concentration of Rp-3 of 40000pppm (by volume).
Application example 1
All examples the evaluation of the oxygen-consuming activity of the catalyst was carried out in a fixed-bed microreactor (quartz tubular reactor having an internal diameter of 6 mm), the amount of the catalyst used was 0.2g, and the reactor inlet gas was controlled at 100 mL/min. The Rp-3 fuel vapor was injected into the vaporization chamber using a 100 series KDS120 micro-syringe pump from Stoelting corporation of america and then mixed with air into the reactor. The amount of gas above an oil tank on the simulated machine per gram of catalyst treated per hour is 30L. The relationship of Rp-3 fuel steam conversion to temperature on all example catalysts is shown in Table 1 when the Rp-3 fuel steam has a hydrocarbon concentration of 20000ppm, an oxygen start concentration of 20 vol%, and the balance nitrogen. As can be seen from Table 1, in addition to the catalysts of examples 2 and 3, the catalysts of the other examples were able to convert 100% of the Rp-3 fuel vapor at a temperature of 180 ℃. Reaction product testing indicates that carbon dioxide and water are the major products, i.e., oxygen in the fuel vapor is reduced stoichiometrically by oxidation. The activity of the bi-component and tri-component noble metal catalysts is better than that of the component noble metal catalyst; the hydrazine hydrate reduction precipitation catalyst has better activity than the hydrogen peroxide reduction precipitation catalyst. The most active catalysts were the catalysts of examples 9 and 10, and essentially complete conversion of the fuel vapor was achieved at 180 ℃.
TABLE 1Rp-3 relationship of fuel vapor hydrocarbon conversion (%) to reaction temperature (. degree. C.) in
Application example 2
The catalyst powders of examples 9 and 10 were coated on the surface of a metal honeycomb carrier to obtain a metal honeycomb catalyst having a honeycomb single column size of 2mm in diameter, 2mm in length and 6.3mL in volume, and the reactor inlet gas was controlled at 2100mL/min (maintaining a space velocity of 2000/h). Rp-3 fuel was injected into the vaporization chamber using a 100 series KDS120 microinjection pump from Stoelting, USA. The relationship between Rp-3 fuel vapor conversion and temperature on the catalysts of examples 9 and 10 is shown in Table 2 when the Rp-3 fuel vapor CH concentration is 20000ppm and 40000ppm, the oxygen start concentration is controlled at 20 vol%, and the remainder is nitrogen. As can be seen from Table 2, both example 9 and example 10 achieve 100% Rp-3 fuel steam reforming at inlet temperatures above 165 deg.C, and the three-component noble metal catalyst (example 10) is more active than the two-component noble metal catalyst (example 9).
TABLE 2 Rp-3 Fuel steam conversion vs. Inlet temperature at Honeycomb catalyst temperature
Application example 3
A fixed bed microreactor (a quartz tubular reactor with the inner diameter of 6 mm) is adopted, the dosage of the catalyst in example 9 and example 10 is 0.2g, the gas at the inlet of the reactor is controlled at 100mL/min, a part of gas enters a saturator filled with Rp-3 fuel through a flow divider, the CH concentration is controlled at 10000ppm, 20000ppm and 40000ppm, the initial oxygen concentration is controlled at 20 volume percent, the gas quantity above an onboard oil tank of a processor per hour per gram of catalyst is 30L, and the reaction pressure is normal pressure. The reaction temperature was controlled at the CH 100% conversion temperature, 180 ℃ and 170 ℃ respectively. And (3) removing water in the gas at the outlet of the reactor through a dryer, keeping the gas flow at 100mL/min through supplementary air, and shunting the gas to enter a saturator of an Rp-3 fuel to form a circulating reaction gas flow. The number of cycles required to reduce the oxygen concentration to below 5% on the catalysts of examples 9 and 10 is shown in table 3. As is clear from Table 3, the catalysts of examples 9 to 10 had 11, 6 and 3 cycles for the hydrocarbon concentrations of 10000ppm, 20000ppm and 40000ppm at the catalyst bed temperatures of 180 ℃ and 170 ℃ respectively.
TABLE 3 relationship between CH concentration and cycle number for oxygen concentration at 100% CH conversion temperature to drop below 5%
Application example 4
The catalysts of example 7, example 8, example 9 and example 10 were evaluated for stability in oxygen-consuming continuous operation. A fixed bed microreactor (a quartz tubular reactor with the inner diameter of 6 mm) is adopted, the using amount of the catalyst is 0.2g, the gas at the inlet of the reactor is controlled at 100mL/min, the gas amount above an onboard oil tank of a processor is 30L per gram of the catalyst per hour, and the reaction pressure is normal pressure. The Rp-3 fuel vapor was injected into the vaporization chamber using a 100 series KDS120 micro-syringe pump from Stoelting corporation of america and then mixed with air into the reactor. The hydrocarbon concentration of Rp-3 fuel steam is controlled at 40000ppm, the initial oxygen concentration is controlled at 10 vol%, the reaction temperature is controlled at 180 ℃, and the stable oxygen consumption efficiency can be maintained on the catalysts of example 7, example 8, example 9 and example 10 within 100 hours of continuous reaction, and the oxygen content is lower than 4 vol%.
Application example 5
The catalysts of example 7, example 8, example 9 and example 10 were evaluated for oxygen consumption stability during the alternate temperature ramp and ramp. A fixed bed micro reactor (a quartz tube reactor with the inner diameter of 6 mm) is adopted, the using amount of the catalyst is 0.2g, the inlet gas of the reactor is controlled at 100mL/min, the gas amount above a processor-carried oil tank per gram of the catalyst per hour is 30L, and the reaction pressure is normal pressure. The Rp-3 fuel vapor was injected into the vaporization chamber using a 100 series KDS120 micro-syringe pump from Stoelting corporation of america and then mixed with air into the reactor. The Rp-3 fuel vapor CH concentration was controlled at 40000ppm and the oxygen start concentration was controlled at 10% by volume. After the reaction is carried out for 5 hours at 190 ℃, the reaction gas is cut off, the temperature of the bed layer is reduced to the room temperature, and the reaction is kept for 8 hours; then introducing reaction gas, raising the temperature of the catalytic bed layer to 190 ℃, reacting for 5h, and circulating for 20 times. In the processes of continuously increasing and decreasing the temperature, the catalysts of example 7, example 8, example 9 and example 10 can maintain stable oxygen consumption efficiency, and the oxygen concentration is below 5. FIG. 2 illustrates the change in oxygen concentration of the reactor outlet gas over time over the catalyst of example 10. The physical data of the catalyst after reaction has no obvious change, and comprises XRD phase analysis, XPS surface element chemical state analysis, deposition element composition analysis and SEM morphology analysis.
The catalyst provided by the invention mainly comprises titanium dioxide and a noble metal and transition metal composite catalyst loaded by the titanium dioxide, wherein the noble metal is one or more of Pt, Pd and Ru metals or oxides, and the transition metal is one or more of Nb, Co, Mn, Zr, Cu and Ce oxides. The titanium dioxide and the loaded noble metal and transition metal composite catalyst thereof have simple preparation process and do not generate secondary pollution; the catalyst can efficiently oxidize Rp-3 fuel steam at low temperature to achieve high oxygen consumption activity; meanwhile, the titanium dioxide is easy to prepare silica sol and alumina sol, and is not easy to fall off after being coated on the metal honeycomb material in a powerful way, and the honeycomb-shaped titanium dioxide and the loaded noble metal and transition metal composite catalyst thereof are suitable for an aircraft fuel tank green inerting system with larger vibration.
While several embodiments of the present invention have been described herein, it will be obvious to those skilled in the art that such embodiments are provided by way of example only. Numerous variations, substitutions and modifications will occur to those skilled in the art without departing from the scope of the invention. It is intended that the following claims define the scope of the invention and that methods and structures within the scope of these claims and their equivalents be covered thereby.
Claims (10)
1. A preparation method of a noble metal and transition metal composite catalyst is characterized by comprising the following steps:
1) dispersing a titanium precursor in ethanol, adding an alkaline precipitator to control the pH value of a titanium precursor solution to be 11-12, carrying out crystallization treatment for 4-8h at the temperature of 110-150 ℃, filtering, drying at the temperature of 80-150 ℃, and roasting at the temperature of 400-600 ℃ to obtain honeycomb-shaped titanium dioxide;
2) adding the titanium dioxide into a mixed solution containing a noble metal precursor and a transition metal precursor, adding a reduction precipitator, carrying out co-precipitation of the noble metal precursor and the transition metal precursor on the surface of the titanium dioxide by a reduction precipitation method, drying, roasting, introducing a reduction gas for reduction roasting, and introducing an oxidation gas for oxidation roasting to obtain the titanium dioxide-loaded noble metal and transition metal composite catalyst.
2. The method according to claim 1, wherein the reductive precipitation agent is at least one selected from the group consisting of hydrogen peroxide, sodium borohydride, and hydrazine hydrate.
3. The production method according to claim 1, wherein the noble metal is at least one selected from the group consisting of Pt, Pd, Ru, Rh metals and oxides, and the noble metal loading is 0 to 5 wt% and is not 0 based on the weight of the catalyst;
the transition metal is at least one of Nb, Co, Mn, Zr, Cu and Ce oxides, and the loading amount of the transition metal is 0-5 wt% and is not 0 based on the weight of the catalyst.
4. The process of claim 3 wherein the noble metal loading is from 0.5 to 3 weight percent, based on the weight of the catalyst.
5. The process of claim 3 wherein the transition metal loading is from 0.5 to 3 wt.% based on the weight of the catalyst.
6. The method as claimed in claim 1, wherein the drying temperature is in the range of 100-120 ℃; the drying atmosphere is air; the roasting temperature range is 400-600 ℃; the roasting atmosphere is air or nitrogen; the temperature range of the reduction roasting is 300-500 ℃; the reducing gas is a gas containing 1-20 vol% of H2N of (A)2(ii) a The temperature range of the oxidizing roasting is 300-500 ℃; the oxidizing gas being an oxidizing gas containing 1-50 vol.% of O2N of (A)2。
7. The production method according to claim 1, characterized in that the precursor of titanium is at least one selected from isopropyl titanate, titanium oxychloride, titanium tetrachloride and titanium sulfate.
8. The method according to claim 1, wherein the noble metal precursor is at least one selected from the group consisting of chloroplatinic acid, ammonium platinate, palladium chloride, palladium nitrate, ruthenium chloride, and ruthenium acetate.
9. The preparation method according to claim 1, characterized in that the transition metal precursor is selected from at least one of ammonium niobium oxalate, niobium pentachloride, niobium oxychloride, cobalt nitrate, cobalt carbonate, cobalt sulfate, manganese nitrate, manganese carbonate, manganese sulfate, zirconium oxychloride, zirconium nitrate, copper sulfate, copper nitrate, cerium nitrate, and cerium acetate.
10. A low-temperature catalytic oxygen elimination method, which is characterized in that the oxygen elimination is carried out by using the noble metal and transition metal composite catalyst prepared by the preparation method of any one of claims 1 to 9 in a green inerting system of an aircraft fuel tank; in the inerting system, the fuel vapor is Rp-3 fuel vapor with CH concentration of 10000-; the concentration of oxygen is 1-20% by volume; the reaction temperature is 115-140 ℃; the gas linear velocity of the catalyst bed is 0.4-14 m/s.
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