CN115430458A - 冷启动催化剂和其在排气系统中的用途 - Google Patents
冷启动催化剂和其在排气系统中的用途 Download PDFInfo
- Publication number
- CN115430458A CN115430458A CN202211131732.5A CN202211131732A CN115430458A CN 115430458 A CN115430458 A CN 115430458A CN 202211131732 A CN202211131732 A CN 202211131732A CN 115430458 A CN115430458 A CN 115430458A
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- Prior art keywords
- catalyst
- cold start
- molecular sieve
- start catalyst
- low temperature
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- 239000003054 catalyst Substances 0.000 title claims abstract description 186
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000002808 molecular sieve Substances 0.000 claims abstract description 65
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 37
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 21
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 19
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 16
- 238000002485 combustion reaction Methods 0.000 claims abstract description 13
- -1 platinum group metals Chemical class 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims description 67
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 238000001179 sorption measurement Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 8
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 7
- 239000010948 rhodium Substances 0.000 claims description 7
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 claims description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 94
- 239000010457 zeolite Substances 0.000 description 22
- 229910021536 Zeolite Inorganic materials 0.000 description 20
- 239000002002 slurry Substances 0.000 description 20
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 238000003860 storage Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 229910052878 cordierite Inorganic materials 0.000 description 5
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 241000264877 Hippospongia communis Species 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000010953 base metal Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004071 soot Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910021065 Pd—Fe Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000005549 size reduction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- GNKTZDSRQHMHLZ-UHFFFAOYSA-N [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] Chemical compound [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] GNKTZDSRQHMHLZ-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229940001007 aluminium phosphate Drugs 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 235000012243 magnesium silicates Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01B—SOIL WORKING IN AGRICULTURE OR FORESTRY; PARTS, DETAILS, OR ACCESSORIES OF AGRICULTURAL MACHINES OR IMPLEMENTS, IN GENERAL
- A01B35/00—Other machines for working soil not specially adapted for working soil on which crops are growing
- A01B35/02—Other machines for working soil not specially adapted for working soil on which crops are growing with non-rotating tools
- A01B35/04—Other machines for working soil not specially adapted for working soil on which crops are growing with non-rotating tools drawn by animal or tractor or man-power
-
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
-
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
- B01D53/9463—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick
- B01D53/9468—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick in different layers
-
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
- B01D53/9477—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on separate bricks, e.g. exhaust systems
-
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9481—Catalyst preceded by an adsorption device without catalytic function for temporary storage of contaminants, e.g. during cold start
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
公开了一种冷启动催化剂。所述冷启动催化剂是有效于在某个低温以下吸附NOx和烃(HC)和在高于所述低温的温度转化和释放吸附的NOx和HC的冷启动催化剂。所述冷启动催化剂包含分子筛催化剂和负载的铂族金属催化剂。所述分子筛催化剂基本上由贵金属和分子筛组成。所述负载的铂族金属催化剂包含一种或多种铂族金属和一种或多种无机氧化物载体。本发明还包括一种包括冷启动催化剂的排气系统,和一种利用冷启动催化剂来处理来自内燃机的废气的方法。
Description
本申请是基于申请号为201480066543.1、申请日为2014年12月8日、发明名称为“冷启动催化剂和其在排气系统中的用途”的中国专利申请的分案申请。
发明领域
本发明涉及冷启动催化剂和其在用于内燃机的排气系统中的用途。
发明背景
内燃机产生了包含各种污染物的废气,包括氮氧化物(“NOx”),一氧化碳和未燃烧的烃,这是政府立法的主题。排放控制系统广泛地用于降低排放到大气的这些污染物的量,一旦它们达到其操作温度(通常为200℃和更高),通常获得非常高的效率。然而,这些系统低于其操作温度(“冷启动”期间)是相对低效的。
随着甚至更严格的国家和区域立法降低了可以从柴油或汽油发动机排放的污染物的量,在冷启动期间降低排放成为主要的挑战。因此,用于降低在冷启动条件过程中排放的NOx和烃的水平的方法持续被探索。
对于冷启动烃控制,调查了基于沸石的烃捕集部件。在这些系统中,在启动期间沸石吸附和储存烃,当排气温度足够高以脱附烃时,释放被储存的烃。然后,当下游催化部件达到其操作温度时,脱附的烃被转化。
对于冷启动NOx控制,尤其是在贫燃条件下,研究了NOx储存和释放催化剂。在升温期间催化剂吸附NOx和在更高的排气温度热脱附NOx。下游催化剂如选择性催化还原(“SCR”)或NOx吸附催化剂(“NAC”)有效地将脱附的NOx还原为氮。
通常,NOx吸附剂材料由用至少一种铂族金属涂覆的无机氧化物例如氧化铝、二氧化硅、二氧化铈、氧化锆、二氧化钛或混合氧化物组成。PCT国际申请WO2008/047170公开了一种系统,其中来自贫燃废气的NOx在低于200℃的温度吸附和然后在高于200℃热脱附。教导NOx吸附剂由钯和铈氧化物或混合氧化物或含铈和至少一种其它过渡金属的混合氧化物或复合氧化物组成。
PCT国际申请WO2004/076829公开了废气纯化系统,其包括设置在SCR催化剂上游的NOx储存催化剂。NOx储存催化剂包含用至少一种铂族金属(Pt,Pd,Rh,或Ir)涂覆或活化的至少一种碱金属、碱土金属或稀土金属。教导特别优选的NOx储存催化剂包含用铂涂覆的氧化铈和此外在基于氧化铝的载体上的铂作为氧化催化剂。EP1027919公开了NOx吸附剂材料,其包含多孔载体材料,例如氧化铝,沸石,氧化锆,二氧化钛,和/或氧化镧,和至少0.1wt%的贵金属(Pt,Pd,和/或Rh)。以负载在氧化铝上的铂为例。
此外,US专利No.5,656,244和5,800,793描述了组合NOx储存/释放催化剂与三元催化剂的系统。教导NOx吸附剂包含铬、铜、镍、锰、钼或钴(除了其它金属以外)的氧化物,其负载在氧化铝、莫来石、堇青石或碳化硅上。PCT国际申请WO03/056150描述了组合低温NO2捕集材料和烟灰过滤器的系统。教导低温NO2捕集材料包含与碱金属阳离子交换的沸石,其中沸石选自ZSM-5、ETS-10、Y-沸石、β沸石、镁碱沸石、丝光沸石、硅酸钛和磷酸铝和贱金属,其选自Mn、Cu、Fe、Co、W、Re、Sn、Ag、Zn、Mg、Li、Na、K、Cs、Nd和Pr。
遗憾地,尤其是在高NOx储存效率下,这种系统的NOx吸附能力不是足够高。因为日益严格的控制由内燃机释放到大气的NOx和烃的量的全球立法,总是存在对于在冷启动条件期间更加有效的废气清洁的需要。为了克服这些问题,美国申请公开No.2012/0308439A1教导冷启动催化剂,其包含(1)包含贱金属、贵金属和沸石的沸石催化剂,和(2)包含一种或多种铂族金属和一种或多种无机氧化物载体的负载的铂族金属催化剂。然而,美国申请公开No.2012/0308439A1需要沸石催化剂组分的贱金属组分。
对于任何汽车系统和方法,希望的是在废气处理系统中获得仍进一步的改善,特别是在冷启动条件下。我们发现了一种提供来自内燃机的废气的增强的清洁的新冷启动催化剂。
发明内容
本发明为有效于在某个低温以下吸附NOx和烃(HC)和在高于所述低温的温度转化和释放吸附的NOx和HC的冷启动催化剂。冷启动催化剂包含分子筛催化剂和负载的铂族金属催化剂。分子筛催化剂基本上由贵金属和分子筛组成。负载的铂族金属催化剂包含一种或多种铂族金属和一种或多种无机氧化物载体。本发明还包括一种包括冷启动催化剂的排气系统,和一种利用冷启动催化剂来处理来自内燃机的废气的方法。冷启动催化剂通过改善的NOx储存和NOx转化、改善的烃储存和转化和改善的CO氧化在冷启动期间有效地降低排放。
具体实施方式
本发明的冷启动催化剂包含分子筛催化剂和负载的铂族金属催化剂。冷启动催化剂有效于在某个低温以下吸附NOx和烃(HC)和在高于所述低温的温度转化和释放吸附的NOx和HC。优选地,低温为约200℃。分子筛催化剂基本上由贵金属和分子筛组成,和优选由贵金属和分子筛组成。贵金属优选为钯、铂、铑、金、银、铱、钌、锇或其混合物;更优选为钯、铂、铑或其混合物。钯是特别优选的。
分子筛可为任何天然或合成分子筛,包括沸石,和优选由铝、硅和/或磷组成。分子筛通常具有通过氧原子共享而连接的SiO4、AlO4和/或PO4的三维设置,但也可以为二维结构。分子筛骨架通常为阴离子型的,其通过电荷补偿阳离子来平衡,通常为碱和碱土元素(例如,Na,K,Mg,Ca,Sr,和Ba),铵离子以及质子。
分子筛优选为最大环尺寸为8个四面体原子的小孔分子筛,最大环尺寸为10个四面体原子的中孔分子筛,或最大环尺寸为12个四面体原子的大孔分子筛。更优选地,分子筛具有AEI、MFI、EMT、ERI、MOR、FER、BEA、FAU、CHA、LEV、MWW、CON、EUO或其混合物的骨架结构。
分子筛催化剂可通过任何已知的方式来制备。例如,贵金属可通过任何已知的方式添加至分子筛以形成分子筛催化剂,添加的方式不认为是特别关键的。例如,贵金属化合物(例如硝酸钯)可通过浸渍、吸附、离子交换、初湿、沉淀等负载在分子筛上。
负载的铂族金属催化剂包含一种或多种铂族金属(“PGM”)和一种或多种无机氧化物载体。PGM可为铂、钯、铑、铱或其组合,和最优选铂和/或钯。无机氧化物载体最通常包括第2、3、4、5、13和14族元素的氧化物。有用的无机氧化物载体优选具有10-700m2/g的表面积,0.1-4mL/g的孔隙体积,和约的孔径。无机氧化物载体优选为氧化铝,二氧化硅,二氧化钛,氧化锆,二氧化铈,氧化铌,钽氧化物,钼氧化物,钨氧化物,或其任何两种或更多种的混合氧化物或复合氧化物,例如二氧化硅-氧化铝,二氧化铈-氧化锆或氧化铝-二氧化铈-氧化锆。氧化铝和二氧化铈是特别优选的。
负载的铂族金属催化剂可通过任何已知的方式来制备。优选地,一种或多种铂族金属通过任何已知的方式负载到一种或多种无机氧化物上以形成负载的PGM催化剂,添加的方式不认为是特别关键的。例如,铂化合物(例如硝酸铂)可通过浸渍、吸附、离子交换、初湿、沉淀等负载在无机氧化物上。其它金属如铁、锰、钴和钡也可以添加至负载的PGM催化剂。
本发明的冷启动催化剂可通过本领域公知的方法来制备。分子筛催化剂和负载的铂族金属催化剂可物理混合以产生冷启动催化剂。优选地,冷启动催化剂进一步包括流通式基材或过滤式基材。在一个实施方案中,分子筛催化剂和负载的铂族金属催化剂涂覆在流通式或过滤式基材上,和优选使用载体涂层程序沉积在流通式或过滤式基材上以产生冷启动催化剂系统。
流通式或过滤式基材是能够包含催化组分的基材。基材优选为陶瓷基材或金属基材。陶瓷基材可由任何适合的耐火材料组成,例如,氧化铝,二氧化硅,二氧化钛,二氧化铈,氧化锆,氧化镁,沸石,氮化硅,碳化硅,锆硅酸盐,镁硅酸盐,铝硅酸盐,金属铝硅酸盐(例如堇青石和锂辉石),或其任何两种或更多种的混合物或混合氧化物。堇青石、镁铝硅酸盐和碳化硅是特别优选的。
金属基材可由任何适合的金属组成,和特别是耐热的金属和金属合金例如钛和不锈钢以及含有铁、镍、铬和/或铝(除了其它痕量金属以外)的铁素体合金。
流通式基材优选为具有蜂窝状结构的流通式整料,所述蜂窝状结构具有多个小、平行的薄壁通道,其轴向穿过基材且从基材的入口或出口贯穿延伸。基材的通道横截面可为任何形状,但是优选正方形、正弦形、三角形、矩形、六边形、梯形、圆形或椭圆形。
过滤式基材优选为壁流式整料过滤器。壁流式过滤器的通道交替封闭,这允许废气物流从入口进入通道,然后流过通道壁,和从通向出口的不同通道离开过滤器。因此,废气物流中的颗粒被捕集在过滤器中。
分子筛催化剂和负载的铂族催化剂可通过任何已知的方式添加至流通式或过滤式基材。使用载体涂层程序制备冷启动催化剂的代表性方法如下文所述。将理解的是,下文的方法可以根据不同的本发明实施方案而变化。而且,将分子筛催化剂和负载的PGM催化剂添加在流通式或过滤式基材上的顺序不认为是关键的。因此,分子筛催化剂可在负载的PGM催化剂之前载体涂覆在基材上,或负载的PGM催化剂可在分子筛催化剂之前载体涂覆在基材上。
预成型的分子筛催化剂可通过载体涂覆步骤添加至流通式或过滤式基材。替代地,可通过将未改性分子筛首先载体涂覆在流通式或过滤式基材上以产生分子筛涂覆的基材来在所述基材上形成分子筛催化剂。然后,可以将贵金属添加至分子筛涂覆的基材,这可通过浸渍程序等完成。
优选通过首先在恰当的溶剂(优选水)中浆化细分的分子筛催化剂(或未改性分子筛)颗粒以形成浆料来进行载体涂覆程序。额外组分例如粘合剂或稳定剂也可以作为水溶性或水分散性化合物的混合物引入浆料。浆料优选包含10-70重量%的固体,更优选20-50重量%。在形成浆料之前,分子筛催化剂(或未改性分子筛)颗粒优选经受尺寸减小处理(例如,研磨),使得固体颗粒的平均粒度为直径小于20微米。
然后,流通式或过滤式基材可一次或多次浸入浆料或浆料可涂覆在基材上,使得希望负载量的催化材料沉积在基材上。如果贵金属没有在载体涂覆流通式或过滤式基材之前引入分子筛,分子筛涂覆的基材通常干燥和煅烧,然后贵金属可通过任何已知的方式添加至分子筛涂覆的基材,包括浸渍、吸附或离子交换,例如,利用贵金属化合物(例如硝酸钯)。优选地,流通式或过滤式基材的整个长度用浆料涂覆,使得分子筛催化剂载体涂层覆盖基材整个表面。
在流通式或过滤式基材用分子筛催化剂浆料涂覆和用贵金属浸渍(如果需要)之后,经涂覆的基材优选干燥和然后通过在升高的温度加热而煅烧以形成分子筛催化剂涂覆的基材。优选地,煅烧在400-600℃进行大约1-8小时。
优选通过首先制备细分的负载的PGM催化剂颗粒在恰当的溶剂(优选水)中的浆料来完成负载的PGM催化剂的载体涂层添加。在形成浆料之前,负载的PGM催化剂颗粒优选经受尺寸减小处理(例如,研磨),使得固体颗粒的平均粒度为直径小于20微米。额外组分例如过渡金属氧化物、粘合剂、稳定剂或促进剂可作为水分散性或水溶性化合物引入浆料中。
分子筛催化剂涂覆的基材然后可一次或多次浸入负载的PGM催化剂浆料或负载的PGM催化剂浆料可涂覆在分子筛催化剂涂覆的基材上,使得希望负载量的催化材料沉积在基材上。
替代地,仅包含无机氧化物的浆料可首先沉积在分子筛催化剂涂覆的基材上以形成无机氧化物涂覆的基材,之后进行干燥和煅烧步骤。然后铂族金属通过任何已知的方式添加至无机氧化物涂覆的基材,包括浸渍、吸附或离子交换铂族金属化合物(例如硝酸铂)。
优选地,流通式或过滤式基材的整个长度用负载的PGM催化剂浆料涂覆,从而负载的PGM催化剂的载体涂层覆盖基材的整个表面。
在流通式或过滤式基材用负载的PGM催化剂浆料涂覆后,优选干燥和然后在升高的温度加热而煅烧以产生冷启动催化剂。优选地,煅烧在400-600℃进行大约1-8小时。
在替代的实施方案中,流通式或过滤式基材包含分子筛催化剂,和负载的铂族金属催化剂涂覆在分子筛催化剂基材上。在这种情况下,分子筛挤出以形成流通式或过滤式基材,和负载的铂族金属催化剂涂覆在挤出的分子筛催化剂流通式或过滤式基材上。分子筛催化剂挤出的基材优选为蜂窝状流通式整料。
挤出的分子筛基材和蜂窝状体以及制备它们的方法在本领域中是已知的。参见例如,美国专利号5,492,883,5,565,394,和5,633,217和美国专利No.Re.34,804。通常,分子筛材料与持久粘合剂如有机硅树脂和临时粘合剂如甲基纤维素混合,和混合物挤出以形成蜂窝状生坯体,其然后煅烧和烧结以形成最终的分子筛基材整料。分子筛可以在挤出之前包含贵金属,使得贵金属/分子筛基材(流通式或过滤器)整料通过挤出程序而产生。
如果分子筛基材整料形成,则分子筛基材整料经受浸渍程序(如果需要)以将贵金属负载在分子筛整料上,之后进行载体涂覆步骤以载体涂覆负载的PGM催化剂。
本发明还包括用于包括冷启动催化剂的内燃机的排气系统。排气系统优选包括一个或多个另外的能够在正常操作温度从内燃机的废气除去污染物的后处理装置。优选地,排气系统包括冷启动催化剂和一种或多种选自以下的其它催化剂部件:(1)选择性催化还原(SCR)催化剂,(2)颗粒过滤器,(3)SCR过滤器,(4)NOx吸附催化剂,(5)三元催化剂,(6)氧化催化剂,或任何其组合。
这些后处理装置在本领域是公知的。选择性催化还原(SCR)催化剂为通过与氮化合物(例如氨或尿素)或烃(贫燃NOx还原)反应将NOx还原为N2的催化剂。典型的SCR催化剂包含氧化钒-二氧化钛催化剂,氧化钒-钨氧化物-二氧化钛催化剂,或金属/沸石催化剂,例如铁/β沸石,铜/β沸石,铜/SSZ-13,铜/SAPO-34,Fe/ZSM-5,或铜/ZSM-5。
颗粒过滤器为减少来自内燃机的排气的颗粒的装置。颗粒过滤器包括催化颗粒过滤器和裸(非催化)颗粒过滤器。催化颗粒过滤器(用于柴油和汽油应用)包括金属和金属氧化物组分(例如Pt,Pd,Fe,Mn,Cu,和二氧化铈)以氧化烃和一氧化碳(除了破坏由过滤器捕集的烟灰之外)。
选择性催化还原过滤器(SCRF)是组合SCR和颗粒过滤器的功能的单一基材装置。它们用于降低来自内燃机的NOx和颗粒排放。除了SCR催化剂涂覆,颗粒过滤器也可以包括其它金属和金属氧化物组分(例如Pt,Pd,Fe,Mn,Cu和二氧化铈)以氧化烃和一氧化碳(除了破坏由过滤器捕集的烟灰之外)。
NOx吸附催化剂(NAC)设计以在贫燃排气条件下吸附NOx,在富燃条件下释放吸附的NOx,和还原释放的NOx以形成N2。NAC通常包括NOx-储存组分(例如,Ba,Ca,Sr,Mg,K,Na,Li,Cs,La,Y,Pr和Nd),氧化组分(优选Pt)和还原组分(优选Rh)。这些组分包含在一种或多种载体上。
三元催化剂(TWC)通常在化学计量条件下用于汽油发动机以在单一装置上将NOx转化为N2,将一氧化碳转化为CO2,以及将烃转化为CO2和H2O。
氧化催化剂和特别是柴油氧化催化剂(DOC)在本领域是公知的。氧化催化剂设计以将CO氧化为CO2以及将气相烃(HC)和柴油颗粒的有机馏分(可溶的有机馏分)氧化为CO2和H2O。典型的氧化催化剂包括在高表面积无机氧化物载体如氧化铝、二氧化硅-氧化铝和沸石上的铂以及任选的钯。
可以构造排气系统,使得冷启动催化剂设置成接近于发动机和额外的后处理装置设置在冷启动催化剂的下游。因此,在正常操作条件下,发动机废气首先流过冷启动催化剂,之后接触后处理装置。替代地,排气系统可以包含阀门或其它气体导向装置,使得在冷启动期间(低于约150-220℃的温度,如在后处理装置处测量)引导废气接触后处理装置,之后流至冷启动催化剂。一旦后处理装置达到操作温度(约150-220℃,如在后处理装置处测量),然后再引导废气流接触冷启动催化剂,之后接触后处理装置。这确保冷启动催化剂的温度保持低,持续更长的时间,因此改善了冷启动催化剂的效率,同时允许后处理装置更快地达到操作温度。美国专利No.5,656,244例如教导了在冷启动和正常操作条件期间控制废气流的装置,该专利的教导通过参考引入本文。
本发明还包括一种处理来自内燃机的废气的方法。该方法包括在某个低温或低于该低温的温度将NOx和烃(HC)吸附在冷启动催化剂上,在高于所述低温的温度转化和热脱附来自冷启动催化剂的NOx和HC,和在冷启动催化剂的下游的催化剂部件上催化除去脱附的NOx和HC。优选地,低温为约200℃。
冷启动催化剂的下游的催化剂部件为SCR催化剂、颗粒过滤器、SCR过滤器、NOx吸附催化剂、三元催化剂、氧化催化剂或其组合。
以下的实施例仅描述本发明。本领域技术人员将认识到在本发明精神和权利要求范围内的多个变型。
实施例1:催化剂的制备
对比催化剂1A:Pd-Fe/β沸石+Pt/Al2O3
β沸石添加至硝酸铁水溶液,之后添加二氧化硅粘合剂以形成浆料。浆料涂覆在流通式堇青石基材上以获得190g/ft3 Fe的铁负载量,将Fe/沸石涂覆的基材干燥,然后在500℃加热而煅烧4小时。然后通过浸渍Pd硝酸盐水溶液将钯添加至Fe/沸石涂覆的基材以获得50g/ft3的Pd负载量,将Pd-Fe/沸石涂覆的基材干燥和在500℃加热而煅烧4小时。
硝酸铂添加至氧化铝颗粒(研磨至直径小于10微米的平均粒度)的水浆料以形成Pt/氧化铝催化剂浆料。然后,Pt/氧化铝催化剂浆料涂覆在Pd-Fe/沸石涂覆的基材上以获得25g/ft3的Pt负载量,和将最终的涂覆基材干燥,和在500℃加热而煅烧4小时以生产催化剂1A(包含50g/ft3 Pd,190g/ft3 Fe,和25g/ft3 Pt)。
催化剂1B:Pd/β沸石+Pt/Al2O3
根据对比催化剂1A的程序制备催化剂1B,除了不添加硝酸铁。
实施例2:测试程序
对流通式催化剂涂覆的堇青石基材的芯样品(2.54cm x8.4cm)测试催化剂。催化剂芯首先在流通条件下在炉中在水热条件(5%H2O,残量为空气)在750℃老化16小时。然后,使用通过调节各废气组分的质量流量来制备的进料气体物流测试芯在实验室反应器中的催化活性。气体流速保持在21.2L min-1,得到气时空速为30,000h-1(GHSV=30,000h-1)。
在贫燃条件下测试催化剂,使用由200ppm NO、200ppm CO、500ppm癸烷(以C1计)、10%O2、5%CO2、5%H2O和余量氮(体积%)组成的合成废气进料物流。催化剂暴露于进料气体物流,首先在80℃的等温入口气体温度持续100秒,然后入口气体温度以100℃/min的升温速率升高至650℃。
表1的结果给出了本发明催化剂1B与对比催化剂1A可比,表明贱金属可以从冷启动催化剂的沸石组分除去,而不影响其催化性能。
总之,本发明的冷启动催化剂系统表现出多个功能,包括(1)低温NOx储存和以高选择性转化为N2;(2)低温烃储存和转化;和(3)改善的CO氧化活性。
表1催化剂1B和对比催化剂1A的比较。
催化剂1B | 对比催化剂1A* | |
在80℃NO<sub>x</sub>储存能力(g NO<sub>2</sub>/L) | 0.32 | 0.34 |
在100秒的最后NO<sub>x</sub>捕集效率(%) | 78 | 78 |
低于200℃累积的NO<sub>x</sub>储存能力(gNO<sub>2</sub>/L) | 0.45 | 0.46 |
低于200℃累积的HC储存和转化效率(%) | 98 | 98 |
低于200℃累积的CO转化效率(%) | 44 | 45 |
*对比实施例。
Claims (16)
1.有效于在某个低温以下吸附NOx和烃(HC)和在高于所述低温的温度转化和释放吸附的NOx和HC的冷启动催化剂,所述冷启动催化剂包含:(1)基本上由贵金属和分子筛组成的分子筛催化剂;和(2)包含一种或多种铂族金属和一种或多种无机氧化物载体的负载的铂族金属催化剂。
2.根据权利要求1所述的冷启动催化剂,其中所述贵金属选自铂、钯、铑、金、银、铱、钌、锇及其混合物。
3.根据权利要求1所述的冷启动催化剂,其中所述贵金属为钯。
4.根据权利要求1-3任一项所述的冷启动催化剂,其中所述分子筛为最大环尺寸为8个四面体原子的小孔分子筛,最大环尺寸为10个四面体原子的中孔分子筛,或最大环尺寸为12个四面体原子的大孔分子筛。
5.根据权利要求4所述的冷启动催化剂,其中所述分子筛具有选自AEI、MFI、EMT、ERI、MOR、FER、BEA、FAU、CHA、LEV、MWW、CON、EUO及其混合物的骨架结构。
6.根据权利要求1-5任一项所述的冷启动催化剂,其中所述一种或多种铂族金属选自铂、钯、铑、铱及其混合物。
7.根据权利要求1-6任一项所述的冷启动催化剂,其中所述一种或多种无机氧化物载体选自氧化铝、二氧化硅、二氧化钛、氧化锆、二氧化铈、氧化铌、钽氧化物、钼氧化物、钨氧化物和其混合氧化物或复合氧化物。
8.根据权利要求1-7任一项所述的冷启动催化剂,其中所述冷启动催化剂涂覆在流通式或过滤式基材上。
9.根据权利要求8所述的冷启动催化剂,其中所述流通式基材为蜂窝状整料。
10.根据权利要求1-7任一项所述的冷启动催化剂,其中将所述分子筛催化剂挤出以形成流通式或过滤式基材,和将所述负载的铂族金属催化剂涂覆在挤出的分子筛催化剂流通式或过滤式基材上。
11.根据权利要求1-10任一项所述的冷启动催化剂,其中所述低温为200℃。
12.包括根据前述权利要求任一项所述的冷启动催化剂的内燃机排气系统。
13.根据权利要求12所述的排气系统,进一步包括选自选择性催化还原(SCR)催化剂、颗粒过滤器、SCR过滤器、NOx吸附催化剂、三元催化剂、氧化催化剂及其组合的催化剂部件。
14.处理来自内燃机的废气的方法,所述方法包括低于某个低温将NOx和HC吸附在前述权利要求任一项所述的冷启动催化剂上,在高于所述低温的温度转化和热脱附来自所述冷启动催化剂的NOx和HC,和在所述冷启动催化剂的下游的催化剂部件上催化除去脱附的NOx和HC。
15.根据权利要求14所述的方法,其中所述低温为200℃。
16.根据权利要求14或权利要求15所述的方法,其中所述冷启动催化剂的下游的催化剂部件选自SCR催化剂、颗粒过滤器、SCR过滤器、NOx吸附催化剂、三元催化剂、氧化催化剂及其组合。
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GB2522978A (en) | 2015-08-12 |
KR102504525B1 (ko) | 2023-02-28 |
GB2522978B (en) | 2016-09-07 |
EP3485964A1 (en) | 2019-05-22 |
CN105792914A (zh) | 2016-07-20 |
RU2692809C1 (ru) | 2019-06-27 |
GB201421742D0 (en) | 2015-01-21 |
EP3077084A1 (en) | 2016-10-12 |
JP2017500194A (ja) | 2017-01-05 |
EP3077084B1 (en) | 2019-02-06 |
KR20160096108A (ko) | 2016-08-12 |
EP3485964B1 (en) | 2022-09-21 |
KR102339265B1 (ko) | 2021-12-14 |
US20150158023A1 (en) | 2015-06-11 |
US11185854B2 (en) | 2021-11-30 |
WO2015085300A1 (en) | 2015-06-11 |
JP6662778B2 (ja) | 2020-03-11 |
KR20210153160A (ko) | 2021-12-16 |
DE102014118090A1 (de) | 2015-06-11 |
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