CN111514905A - Noble metal and transition metal composite catalyst and preparation method thereof - Google Patents
Noble metal and transition metal composite catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN111514905A CN111514905A CN202010363029.1A CN202010363029A CN111514905A CN 111514905 A CN111514905 A CN 111514905A CN 202010363029 A CN202010363029 A CN 202010363029A CN 111514905 A CN111514905 A CN 111514905A
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- catalyst
- transition metal
- noble metal
- temperature
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- 239000003054 catalyst Substances 0.000 title claims abstract description 110
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 48
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 44
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 43
- 239000002905 metal composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 48
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002828 fuel tank Substances 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 239000000446 fuel Substances 0.000 claims description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 30
- 239000001301 oxygen Substances 0.000 claims description 30
- 229910052760 oxygen Inorganic materials 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 25
- 239000002243 precursor Substances 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 24
- 229910052763 palladium Inorganic materials 0.000 claims description 22
- 229910052697 platinum Inorganic materials 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 18
- 239000011572 manganese Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 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 15
- 229910052707 ruthenium Inorganic materials 0.000 claims description 15
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 229910052718 tin Inorganic materials 0.000 claims description 13
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 11
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 11
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 230000002860 competitive effect Effects 0.000 claims description 6
- 230000008030 elimination Effects 0.000 claims description 6
- 238000003379 elimination reaction Methods 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 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 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 238000010405 reoxidation reaction Methods 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 150000000703 Cerium Chemical class 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 239000012696 Pd precursors Substances 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 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
- 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
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 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
- 239000012716 precipitator Substances 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
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000003463 adsorbent Substances 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 238000011946 reduction process Methods 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 16
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 229910001868 water Inorganic materials 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 230000036284 oxygen consumption Effects 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 229910008839 Sn—Ti Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- -1 benzene aromatic hydrocarbon Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 238000000520 microinjection Methods 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
- 238000009834 vaporization Methods 0.000 description 4
- 230000008016 vaporization Effects 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 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
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 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
- 150000001924 cycloalkanes Chemical class 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
- 238000007598 dipping method 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
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 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
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000008707 rearrangement Effects 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
- 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
- 238000010792 warming Methods 0.000 description 1
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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
- 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
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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
- B01J23/38—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
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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
- B01J23/38—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
-
- B01J35/23—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
Abstract
The invention belongs to the technical field of airplane safety engineering, and particularly relates to a noble metal and transition metal composite catalyst and a preparation method thereof. The catalyst is applied to an aircraft fuel tank green inerting system, and is characterized in that the composite catalyst takes nano cerium oxide as a carrier and precious metal and transition metal as loads. The invention solves the problem that the technical requirement of an airborne oil tank catalytic inerting system cannot be met.
Description
Technical Field
The invention belongs to the technical field of airplane safety engineering, and particularly relates to a noble metal and transition metal composite catalyst and a preparation method thereof.
Background
With the development of aviation industry all over the world, the problem of flight safety is increasingly highlighted. In an aircraft safety accident, the explosion of an onboard fuel tank accounts for a high proportion, so how to inert the onboard fuel tank in a green way becomes one of the focuses of the aircraft safety, and in recent years, many airlines in developed countries develop researches on an onboard fuel tank inerting system. 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.
China has made a series of remarkable and significant progress internationally in aircraft manufacturing, however, the on-board fuel tank inerting system is still in an undeveloped state, and no progress reports on any basis or application basis exist. 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.
National RP-3 aviation kerosene simulation expressible as C9.75H20.52I.e. with C as the main component9、C10、C11. 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). The fuel vapor and oxygen concentrations in the fuel tank may be in the explosive range due to the introduction of external air due to the reduction in the fuel tank level or the change in the air flow caused by fuel consumption. 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 the catalyst, so that the catalyst is carbonized and inactivated. 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: the noble metal and transition metal composite catalyst and the preparation method thereof are provided to solve the problem that the technical requirement of an airborne fuel tank catalytic inerting system cannot be met.
The first aspect provides a noble metal and transition metal composite catalyst, which is applied to an aircraft fuel tank green inerting system, wherein the composite catalyst takes nano cerium oxide as a carrier and noble metal and transition metal as a load;
the noble metal is one or more of Pt, Pd, Ru and Rh metals or oxides, and the loading amount of the noble metal is 0-5 wt% based on the weight of the catalyst;
the transition metal is one or more of oxides of Ti, Co, Mn, Zr, Ce and Sn, and the loading amount of the transition metal is 0-5 wt% based on the weight of the catalyst.
The noble metal is one or more of Pt, Pd, Ru and Rh metals or oxides, and the loading amount of the noble metal is 0.5-3 wt% based on the weight of the catalyst.
The transition metal is one or more of oxides of Ti, Co, Mn, Zr, Ce and Sn, and the loading amount of the transition metal is 0.5-3 wt% based on the weight of the catalyst.
In a second aspect, a method for preparing a noble metal-transition metal composite catalyst is provided, which comprises:
the nano cerium oxide is used as a catalyst carrier, noble metal and transition metal precursor aqueous solution or alcohol solution is loaded by a competitive adsorption impregnation method, and the nano cerium oxide loaded noble metal and transition metal composite catalyst is obtained by drying, roasting, reducing and roasting.
Further comprising:
controlling the pH value of the cerium salt aqueous solution to be 12-14 by adopting an alkaline precipitator such as urea, ammonia water, NaOH aqueous solution and the like, carrying out crystallization treatment for 5-15h at the temperature of 140 ℃ under the temperature of 100-.
The preparation process adopts competitive adsorption dipping method, and the competitive adsorbent is at least one of oxalic acid, citric acid and tartaric acid.
The temperature range of the drying process is 80-150 ℃; the drying atmosphere is air; the temperature range of the roasting process is 350-550 ℃; the roasting atmosphere is air or nitrogen; the temperature range of the reduction process is 200-300 ℃; the reducing gas is 1% -20% H2/N2(ii) a The temperature range of the reoxidation process is 300-500 ℃; the oxidizing gas is in the range of 1-50% O2/N2。
The Pt precursor in 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 precursor of Ti in the transition metal is selected from one of titanium sulfate, tetrabutyl titanate and titanium isopropoxide; 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 tin is selected from stannous sulfate, stannous chloride and stannic chloride.
In a third aspect, a method for low-temperature catalytic elimination of oxygen is provided, comprising:
a noble metal and transition metal composite catalyst is used in an aircraft fuel tank green inerting system for oxygen elimination; the inerting system; wherein the fuel vapor is RP-3 fuel vapor, and the CH concentration is 10000-50000 ppm; 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 nano cerium oxide 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 nano cerium oxide 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 simulated airborne oil tanks with different RP-3 fuel steam concentrations is carried out in a fixed bed reactor. At the catalyst bed temperature of 115-140 ℃, RP-3 fuel steam can be completely converted into CO2And H2O; water vapor and CO at different concentrations2In the presence of the catalyst, the nano cerium oxide supported noble metal and transition metal composite catalyst still maintains the excellent performance. The catalyst of the invention has the advantages of having the effect of reacting medium chain alkane and cycloalkane in RP-3 fuel steamAnd fuel components such as aromatic hydrocarbon and the like have high oxidation activity and high oxygen consumption efficiency; in the stability test of repeated cyclic application, the stable oxygen consumption efficiency can be kept.
The nano cerium oxide loaded noble metal and transition metal composite catalyst has simple preparation process and does not generate secondary pollution; the nano cerium oxide 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 larger vibration.
Drawings
FIG. 1 is a graph showing the change with time of the residual oxygen concentration after the reaction on the catalyst of example 10 under the conditions of an RP-3 fuel vapor CH concentration of 40000ppm by volume, an initial oxygen concentration of 10% by volume, and a temperature of 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 RP-3 fuel vapor CH concentration of 40000pppm (by volume).
Detailed Description
According to one aspect of the invention, a nano cerium oxide loaded noble metal and transition metal composite catalyst for an aircraft fuel tank green inerting system is provided. 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 a nano cerium oxide material prepared by a hydrothermal synthesis method as a carrier, uses an impregnation method to load a noble metal and transition metal precursor aqueous solution or alcohol solution, and obtains the nano cerium oxide loaded noble metal and transition metal composite catalyst by drying, roasting, reducing and roasting.
The precursor of the nano cerium oxide carrier can be one of cerium nitrate, cerium acetate, ammonium cerium nitrate and cerium sulfate;
the preparation method of the nano cerium oxide 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 12-14, carrying out crystallization treatment for 5-15h at the temperature of 140 ℃ under 100-;
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 selected from one or more of oxides of Ti, Co, Mn, Zr, Cu and Sn, more preferably a combination of two or more of oxides of Ti, Co, Mn, Zr, Cu and Sn, and the content of the transition metal is 0-5 wt%, preferably 0.5-3 wt% based on the weight of the metal;
the precursor of the transition metal Ti is selected from one of titanium sulfate, tetrabutyl titanate and titanium isopropoxide; 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 tin is selected from stannous sulfate, stannous chloride and stannic chloride;
the preparation process of the nano cerium oxide loaded noble metal and transition metal composite catalyst adopts drying and roasting treatment, wherein the drying temperature is 80-150 ℃, and more preferably 100-120 ℃; the drying atmosphere is air; the roasting temperature is 350-550 ℃, and more preferably 400-500 ℃; the roasting atmosphere can be air or nitrogen, and is better air;
the nano cerium oxide loaded noble metal and transition metal composite catalyst is subjected to reduction and reoxidation treatment in the preparation process, wherein the reduction temperature is 200-300 ℃, and is better at 250 ℃; the reducing gas may be 1% -20% H2/N2More preferably 1% to 5% H2/N2(ii) a The reoxidation temperature may be 30 deg.C0 to 500 ℃, preferably 400 ℃; the oxidizing gas may be 1% -50% O2/N2More preferably 10% to 25% O2/N2。
Example 1
10g of cerium nitrate is dissolved in 40mL of deionized water, 3g of urea is added, and the mixture is placed in a stainless steel reaction kettle with a 50mL polytetrafluoroethylene substrate and treated for 5 hours at 140 ℃. After cooling to room temperature, filtering, washing the precipitate with deionized water, and drying the precipitate at 100 ℃ 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 nano cerium oxide carrier material is obtained.
3mL of palladium chloride and cobalt nitrate aqueous solution (Pd concentration is 20g/L, cobalt nitrate concentration is 124g/L) is measured and poured into a container filled with 12g of the prepared nano cerium oxide carrier, the mixture is repeatedly stirred until the surface of the cerium oxide carrier is uniformly wet, the mixture is stood in the air for 6 hours, then dried at 110 ℃ overnight, and then put into a muffle furnace, the temperature is raised from 50 ℃ to 450 ℃ in the air atmosphere at the temperature raising rate of 2 ℃/min, 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 Pd-Co/CeO2The catalyst had a Pd content of 0.5 wt% and a Co content of 1 wt%.
Example 2
10g of cerium acetate is dissolved in 40mL of deionized water, 3g of urea is added, and the mixture is placed in a stainless steel reaction kettle with a 50mL polytetrafluoroethylene substrate and treated for 5 hours at 140 ℃. After cooling to room temperature, filtering, washing the precipitate with deionized water, and drying the precipitate at 100 ℃ 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 nano cerium oxide carrier material is obtained.
6mL of ruthenium chloride and manganese nitrate aqueous solution (the concentration of Ru is 20g/L, the concentration of manganese nitrate is 130g/L) is measured and poured into a container filled with 12g of the prepared nano cerium oxide carrier, the mixture is repeatedly stirred until the surface of the cerium oxide carrier is uniformly wet, the mixture is stood in the air for 6h and then dried at 110 ℃ overnight, and then the mixture is put into a muffle furnace, and the temperature is raised at the rate of 2 ℃/min in the air atmosphereHeating to 450 ℃ at 50 ℃, and preserving heat 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 Ru-Mn/CeO2Catalyst with a Ru content of 1 wt% and a Mn content of 2 wt%.
Example 3
10 ceric ammonium nitrate was dissolved in 40mL of deionized water, 3g of urea was added, and the mixture was placed in a 50mL stainless steel reactor 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 100 ℃ 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 nano cerium oxide carrier material is obtained.
6mL 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 12g of the prepared nano cerium oxide carrier, the mixture is repeatedly stirred until the surface of the cerium oxide carrier is uniformly wet, the mixture is stood in the air for 6 hours, then dried at 120 ℃ overnight, then placed into a muffle furnace, and heated from 50 ℃ to 450 ℃ at the heating rate of 2 ℃/min in the air atmosphere, and the temperature is kept for 4 hours. 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/CeO2The catalyst had a content of both Ru and Pd of 1 wt% and a content of Mn of 1 wt%.
Example 4
6mL 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 12g of the nano cerium oxide carrier prepared in the example 1, the mixture is repeatedly stirred until the surface of the cerium oxide carrier is uniformly wet, the mixture is stood in the air for 6 hours, then dried at 120 ℃ overnight, and then put into a muffle furnace, and the temperature is raised from 50 ℃ to 450 ℃ at the temperature raising rate of 2 ℃/min in the air atmosphere and is kept 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 preserving heat for 4h to obtain Pt-Pd-Mn/CeO2A catalyst in which the Pt and Pd contents are each 1% by weight,the Mn content was 1 wt%.
Example 5
6mL of chloroplatinic acid, palladium chloride and titanium sulfate aqueous solution (the concentration of Pt and Pd are both 20g/L and the concentration of titanium sulfate is 200g/L) are measured and poured into a container filled with 12g of the nano cerium oxide carrier prepared in the example 1, the mixture is repeatedly stirred until the surface of the cerium oxide carrier is uniformly wet, the mixture is stood in the air for 6 hours, then dried at 120 ℃ overnight, and then put into a muffle furnace, and the temperature is raised from 50 ℃ to 450 ℃ at the temperature raising rate of 2 ℃/min in the air atmosphere and 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 Pt-Pd-Ti/CeO2Catalyst, wherein the Pt and Pd contents are both 1 wt% and the Ti content is 1 wt%.
Example 6
6mL of ruthenium chloride, chloroplatinic acid, palladium chloride and titanium sulfate hydroalcoholic solution (the concentration of Ru, Pt and Pd is 20g/L, the concentration of titanium sulfate is 200g/L, and the weight ratio of water to alcohol is 1) are weighed and poured into a container filled with 12g of the nano cerium oxide carrier prepared in the embodiment 1, the mixture is repeatedly stirred until the surface of the cerium oxide carrier is uniformly wet, the mixture is statically placed in the air for 6 hours, then dried at 120 ℃ for overnight, then placed into a muffle furnace, and heated from 50 ℃ to 450 ℃ at the heating 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-Ti/CeO2The catalyst contains 1 wt% of Ru, Pt and Pd and 1 wt% of Ti.
Example 7
6mL of ruthenium chloride, chloroplatinic acid, stannous sulfate and titanium sulfate hydroalcoholic solution (the concentration of Ru and Pt is 20g/L, the concentration of stannous sulfate and titanium sulfate is 72g/L and 100g/L respectively, and the weight ratio of water to alcohol is 1) are weighed and poured into a container filled with 12g of the nano cerium oxide carrier prepared in the embodiment 1, the mixture is repeatedly stirred until the surface of the cerium oxide carrier is uniformly wet, the mixture is statically placed in the air for 6 hours, then dried at 120 ℃ overnight, then placed into a muffle furnace, and heated from 50 ℃ to 450 ℃ at the heating 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-Sn-Ti/CeO2The catalyst contains Ru and Pt in an amount of 1 wt% and Sn and Ti in an amount of 2 wt% and 1 wt%, respectively.
Example 8
6mL of palladium chloride, chloroplatinic acid, stannous sulfate, titanium sulfate and citric acid aqueous solution (the concentration of Pd and Pt is 20g/L, the concentration of stannous sulfate and titanium sulfate is 72g/L and 100g/L respectively) are measured and poured into a container containing 6g of the nano cerium oxide carrier prepared in the embodiment 1, the mixture is repeatedly stirred until the surface of the cerium oxide carrier is uniformly wet, the mixture is statically placed in the air for 6 hours, then dried at 120 ℃ for overnight, then placed into a muffle furnace, and heated from 50 ℃ to 450 ℃ at the heating 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 Pd-Pt-Sn-Ti/CeO2The catalyst contains Pd and Pt in an amount of 1 wt% and Sn and Ti in an amount of 2 wt% and 1 wt%, respectively.
Example 9
6mL of palladium chloride, chloroplatinic acid, stannous sulfate and titanium sulfate hydroalcoholic solution (the concentrations of Pd and Pt are both 20g/L, the concentrations of stannous sulfate and titanium sulfate are respectively 72g/L and 100g/L, and the weight ratio of water to alcohol is 1) are measured and poured into a container filled with 12g of the nano cerium oxide carrier prepared in the embodiment 1, the mixture is repeatedly stirred until the surface of the cerium oxide carrier is uniformly wet, the mixture is statically placed in the air for 6 hours, then dried at 120 ℃ overnight, then placed into a muffle furnace, and heated from 50 ℃ to 450 ℃ at the heating 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 Pd-Pt-Sn-Ti/CeO2Catalyst, wherein the Pd and Pt contents are 1 wt% and the Sn and Ti contents are 2 wt%, 1 wt%, respectively.
Example 10
6mL of ruthenium chloride, palladium chloride, chloroplatinic acid, stannous sulfate and titanium sulfate hydroalcoholic solution (the concentrations of Ru, Pd and Pt are 20g/L, the concentrations of stannous sulfate and titanium sulfate are 72g/L and 100g/L respectively, and the weight ratio of water to alcohol is 1) are weighed and poured into the reactorIn a container containing 12g of the nano cerium oxide carrier prepared in example 1, the mixture was repeatedly stirred until the surface of the cerium oxide carrier was uniformly wetted, allowed to stand in air for 6 hours, dried at 120 ℃ overnight, and then placed in a muffle furnace, heated from 50 ℃ to 450 ℃ at a heating rate of 2 ℃/min in air, and then kept warm 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-Pd-Pt-Sn-Ti/CeO2The catalyst contains 1 wt% of Ru, Pd and Pt and 2 wt% and 1 wt% of Sn and Ti, 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 had a residual oxygen concentration as a function of time after 20 cycles at a CH concentration of 40000pppm (by volume) of RP-3 fuel vapor as shown in FIG. 2.
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 microinjection pump from Stoelting corporation, usa, 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 RP-3 fuel vapor conversion vs. temperature for all example catalysts is shown in Table 1 when the RP-3 fuel vapor has a hydrocarbon concentration of 20000ppm, an oxygen start concentration of 20% by volume, 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 catalyst has better activity than the catalyst impregnated by aqueous alcohol solution. The most active catalysts were the catalysts of examples 9 and 10, and essentially complete conversion of fuel vapor was achieved at 170 ℃.
TABLE 1 relationship of RP-3 fuel vapor hydrogen conversion (%) to reaction temperature (. degree. C.)
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 RP-3 fuel vapor conversion vs. 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% by volume, and the remainder is nitrogen. As can be seen from Table 2, the RP-3 fuel vapor conversion reached 100% for examples 9 and 10 at inlet temperatures above 165 ℃ and the three-component noble metal catalyst (example 10) was more active than the two-component noble metal catalyst (example 9).
TABLE 2 RP-3 Fuel steam conversion vs. Inlet temperature relationship over 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 water in the gas at the outlet of the reactor is removed through a dryer, the gas flow is kept at 100mL/min through supplementary air, and the gas is divided and enters a saturator of the 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 microinjection pump from Stoelting corporation, usa, 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 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 microinjection pump from Stoelting corporation, usa, 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 nano cerium oxide and a noble metal and transition metal composite catalyst loaded by the nano cerium oxide, 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 Ti, Co, Mn, Zr, Cu and Sn oxides. The preparation process of the nano cerium oxide and the supported noble metal and transition metal composite catalyst is simple, and no secondary pollution is generated; the catalyst can oxidize RP-3 fuel steam at low temperature and high efficiency to reach high oxygen consumption activity; meanwhile, the nano cerium oxide is easy to prepare silica sol and alumina sol, and is not easy to fall off when being coated on a metal honeycomb material in a powerful way, and the honeycomb nano cerium oxide and the noble metal and transition metal composite catalyst loaded by the same 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 noble metal and transition metal composite catalyst is applied to an aircraft fuel tank green inerting system and is characterized in that the composite catalyst takes nano cerium oxide as a carrier and noble metal and transition metal as a load;
the noble metal is one or more of Pt, Pd, Ru and Rh metals or oxides, and the loading amount of the noble metal is 0-5 wt% based on the weight of the catalyst;
the transition metal is one or more of oxides of Ti, Co, Mn, Zr, Ce and Sn, and the loading amount of the transition metal is 0-5 wt% based on the weight of the catalyst.
2. The catalyst of claim 1 wherein the noble metal is one or more of Pt, Pd, Ru, Rh metal or oxide and the noble metal loading is 0.5 to 3 wt% based on the weight of the catalyst.
3. The catalyst of claim 1, wherein the transition metal is one or more oxides of Ti, Co, Mn, Zr, Ce, Sn, and wherein the transition metal loading is 0.5 to 3 wt% based on the weight of the catalyst.
4. A preparation method of a noble metal and transition metal composite catalyst is characterized by comprising the following steps:
the nano cerium oxide is used as a catalyst carrier, noble metal and transition metal precursor aqueous solution or alcohol solution is loaded by a competitive adsorption impregnation method, and the nano cerium oxide loaded noble metal and transition metal composite catalyst is obtained by drying, roasting, reducing and roasting.
5. The method of claim 4, further comprising:
controlling the pH value of the cerium salt aqueous solution to be 12-14 by adopting an alkaline precipitator such as urea, ammonia water and NaOH aqueous solution, carrying out crystallization treatment for 5-15h at the temperature of 100-140 ℃, filtering, drying at the temperature of 100-120 ℃, and roasting at the temperature of 400-600 ℃ to obtain the nano cerium oxide.
6. The preparation method of claim 4, wherein the preparation process adopts a competitive adsorption impregnation method, and the competitive adsorbent is at least one of oxalic acid, citric acid and tartaric acid.
7. The method of claim 5, wherein the drying process temperature is in the range of 80-150 ℃; the drying atmosphere is air; the temperature range of the roasting process is 350-550 ℃; the roasting atmosphere is air or nitrogen; the temperature range of the reduction process is 200-300 ℃; the reducing gas is 1% -20% H2/N2(ii) a The temperature range of the reoxidation process is 300-500 ℃; the oxidizing gas is in the range of 1-50% O2/N2。
8. The method according to claim 4, wherein the precursor of Pt in noble metal is selected from chloroplatinic acid, ammonium platinate; the Pd precursor is selected from palladium chloride and palladium nitrate; the Ru precursor is selected from ruthenium chloride and ruthenium acetate.
9. The preparation method according to claim 4, wherein the Ti precursor in the transition metal is selected from one of titanium sulfate, tetrabutyl titanate and titanium isopropoxide; 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 tin is selected from stannous sulfate, stannous chloride and stannic chloride.
10. A method for low-temperature catalytic elimination of oxygen is characterized by comprising the following steps:
a noble metal and transition metal composite catalyst is used in an aircraft fuel tank green inerting system for oxygen elimination; the inerting system; wherein the fuel vapor is RP-3 fuel vapor, and the CH concentration is 10000-50000 ppm; 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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