CN106794447A - Catalyst with improved hydrothermal stability - Google Patents
Catalyst with improved hydrothermal stability Download PDFInfo
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- CN106794447A CN106794447A CN201580045670.8A CN201580045670A CN106794447A CN 106794447 A CN106794447 A CN 106794447A CN 201580045670 A CN201580045670 A CN 201580045670A CN 106794447 A CN106794447 A CN 106794447A
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- catalyst
- ceria
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- oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 50
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002245 particle Substances 0.000 claims abstract description 28
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000032683 aging Effects 0.000 claims abstract description 20
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 12
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 38
- 229910052788 barium Inorganic materials 0.000 claims description 21
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 16
- 229910052593 corundum Inorganic materials 0.000 claims description 15
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 15
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- 230000008859 change Effects 0.000 claims description 11
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 10
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical group [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 229910052703 rhodium Inorganic materials 0.000 claims description 8
- 239000010948 rhodium Substances 0.000 claims description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 241000790917 Dioxys <bee> Species 0.000 claims description 3
- NTWUDWUVKKRQRK-UHFFFAOYSA-N aluminum;cerium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Ce+3] NTWUDWUVKKRQRK-UHFFFAOYSA-N 0.000 claims description 3
- -1 aluminum oxide Compound Chemical class 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 235000019580 granularity Nutrition 0.000 description 31
- 239000000463 material Substances 0.000 description 27
- 239000000758 substrate Substances 0.000 description 27
- 239000000446 fuel Substances 0.000 description 19
- 239000002585 base Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000004071 soot Substances 0.000 description 6
- 230000006641 stabilisation Effects 0.000 description 6
- 238000011105 stabilization Methods 0.000 description 6
- 238000011144 upstream manufacturing Methods 0.000 description 5
- 238000003991 Rietveld refinement Methods 0.000 description 4
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 239000013618 particulate matter Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000003870 refractory metal Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910025794 LaB6 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PDNNQADNLPRFPG-UHFFFAOYSA-N N.[O] Chemical compound N.[O] PDNNQADNLPRFPG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- JAOUWIRMVTUUAR-UHFFFAOYSA-N [O-2].[Ti+4].[O-2].[Ce+3].[O-2].[Al+3] Chemical compound [O-2].[Ti+4].[O-2].[Ce+3].[O-2].[Al+3] JAOUWIRMVTUUAR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- VCRLKNZXFXIDSC-UHFFFAOYSA-N aluminum oxygen(2-) zirconium(4+) Chemical compound [O--].[O--].[Al+3].[Zr+4] VCRLKNZXFXIDSC-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229940044927 ceric oxide Drugs 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 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 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910010271 silicon carbide 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
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
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- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9422—Processes characterised by a specific catalyst for removing nitrogen oxides by NOx storage or reduction by cyclic switching between lean and rich exhaust gases (LNT, NSC, NSR)
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
- F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
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- 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
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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Abstract
Disclose the catalyst for processing exhaust emission.The catalyst can include the ceria aluminium oxide particles with the ceria phase existed by the compound weight percentage of about 20% to about 80% based on oxide, the alkaline earth metal component being supported on the ceria aluminium oxide particles, wherein CeO2With hydrothermally stable and with N2In 2%O2It is less than after aging 5 hours at 950 DEG C with 10% steamAverage crystallite granularity microcrystalline form exist.
Description
Technical field
The present invention relates to exhaust emission control catalyst and its application method.The present invention relates more specifically to resistant to heat aging catalyst
With the method using the material.The exhaust emission control catalyst can be used to process exhaust stream, especially be discharged by lean-combustion engine
Those.
Background
The user that operates to of lean-combustion engine, such as diesel engine and gasoline engine provides excellent fuel economy simultaneously
There is the low emission of gas phase hydrocarbon and carbon monoxide because they run under the conditions of lean fuel under air/fuel ratio high.In addition, bavin
Oil machine is provided better than gasoline (spark point in its fuel economy, durability and its under the low speed in terms of the ability of generation high torque
Fire) engine remarkable advantage.
But, from from the point of view of emission, diesel engine there is a problem of more serious than their spark ignition opponent.Due to
Diesel exhaust gas is multiphase mixture, and emission problem is related to particulate matter (PM), nitrogen oxides (NOx), unburned hydrocarbon (HC) and an oxygen
Change carbon (CO).
Nitrogen oxides (the NO from lean-combustion engine must be reducedx) discharge to meet Abgasgesetz standard.Traditional triple effect
Conversion (TWC) automobile catalyst is applied to the row for eliminating the engine run under the conditions of equal or close to stoichiometric air-fuel ratio
NO in gasx, carbon monoxide (CO) and hydrocarbon (HC) pollutant.Produce the definite air-fuel ratio of stoichiometric condition with carbon in fuel and
The relative scale of hydrogen and become.14.65:1 air-fuel ratio (A/F) (air weight/weight of fuel) be with average formula be CHl.88
Hydrocarbon fuel, the corresponding stoichiometric proportion of burning of such as gasoline.Therefore represented the specific A/F ratios of given fuel using sign of lambda
Divided by stoichiometry A/F than result, therefore λ=1 is stoichiometric mixture, λ>1 is lean combustion mixture, and λ<1 is fuel-rich
Mixture.
Used as fuel economy measure, engine, the gasoline-fueled engine in particular for car etc. just sets
Count into and run under lean burn conditions.Such alternate-engine is referred to as " lean-combustion engine ".That is, starting to such
Air-fuel ratio in the ignition mixture of machine supply is maintained at more than stoichiometric proportion so that gained is vented the oxygen of " dilute ", the i.e. exhaust
Content is of a relatively high.Although lean-combustion engine provides advanced fuel economy, their shortcoming is due in exhaust
Oxygen excess, traditional TWC catalyst can not effectively reduce the NO from such enginexDischarge.Overcome the trial of this problem
Including using NOxTrap.The exhaust of such engine passes through catalyst/NOxAdsorbent is processed, the catalyst/NOxAbsorption
Agent stores NO during (oxygen-enriched) operation of lean-burnxAnd stored NO is discharged during fuel-rich (fuel-rich) runsx.It is fuel-rich (or
Stoichiometry) operation during, the catalyst/NOxThe catalytic component of adsorbent promotes NOxBy NOx(including from NOxAdsorbent
The NO of middle releasex) it is reduced into nitrogen with the reaction of HC, CO and/or hydrogen present in exhaust.
In reducing environment, lean-burn NOxTrap (LNT) is by promoting steam reforming reaction and the Water gas shift/WGS of hydrocarbon
(WGS) reaction and priming reaction are providing H2As reducing agent eliminating NOx.Water gas shift reaction be wherein carbon monoxide with
Vapor reacts the chemical reaction to form carbon dioxide and hydrogen.The presence catalysis WGS of the ceria in LNT reacts to change
Enter LNT to SO2The tolerance and stabilization PGM of deactivation；Ceria in LNT also functions as NOxStorage component.
It has been reported that comprising being fixed to ceria (CeO2) on barium (BaCO3) NOxStorage material, and these
NOxMaterial has shown improved thermal ageing property.But, ceria at high temperature hydrothermal aging when there is serious sintering.
The sintering not only causes low temperature NOxStorage volume and WGS activity are reduced, and also result in BaCO3With PGM by body (bulk) CeO2Bag
Envelope.Accordingly, it would be desirable to the catalyst containing ceria of hydrothermally stable.
General introduction
The embodiment of the first aspect of the present invention is related to a kind of catalyst.In the first embodiment, the catalyst
Comprising the dioxy with the ceria phase existed by the particle weight percentage of about 20% to about 80% based on oxide
Change cerium-aluminium oxide particles, the alkaline earth metal component being supported on the ceria-alumina particle, wherein CeO2With hydro-thermal
Stablize and with N2In 2%O2It is less than after aging 5 hours at 950 DEG C with 10% steamAverage crystallite
The microcrystalline form of degree is present.
In this second embodiment, the catalyst of the first embodiment is improved, wherein the alkaline earth metal component is included
Barium component.
In the 3rd embodiment, the catalyst of the second embodiment is improved, wherein the barium component is selected from barium monoxide
And barium carbonate.
In the 4th embodiment, the catalyst of the first to the 3rd embodiment is improved, wherein the ceria-oxygen
Change the compound that aluminum particulate is ceria and aluminum oxide.
In the 5th embodiment, the catalyst of first to fourth embodiment is improved, it further includes and is supported on
At least one platinum group metal selected from platinum, palladium, rhodium, iridium and its mixture on the ceria-alumina particle.
In a sixth embodiment, improve the catalyst of the 5th embodiment, wherein the platinum group metal be selected from platinum,
Palladium, rhodium and its mixture.
In the 7th embodiment, the catalyst of the second to the 6th embodiment is improved, wherein the barium component is pressing
The amount of the weight of weight % to 50 % of oxide meter about 0.5 is present.
In the 8th embodiment, the catalyst of the second to the 7th embodiment is improved, wherein the barium component is pressing
The amount of the weight of weight % to 30 % of oxide meter about 5 is present.
In the 9th embodiment, the catalyst of the 4th embodiment, wherein CeO are improved2And Al2O3Compound contain
There is the ceria of the amount based on the weight % of oxide meter about 30 to 80.
In the tenth embodiment, the catalyst of the 4th embodiment, wherein CeO are improved2And Al2O3Compound contain
There is the ceria of the amount based on the weight % of oxide meter about 50 to 80.
In the 11st embodiment, the catalyst of the 5th or the 6th embodiment is improved, wherein the platinum group metal
Substantially it is made up of platinum and palladium.
In the 12nd embodiment, the catalyst of the 5th or the 6th embodiment is improved, wherein the platinum group metal
Substantially it is made up of platinum.
In the 13rd embodiment, the catalyst of the first to the 12nd embodiment is improved, wherein the catalyst
Selected from three-way catalyst (TWC), diesel oxidation catalyst (DOC), gasoline engine particulate filter (GPF), lean-burn NOxTrap
(LNT), integrated lean-burn NOxTrap-three-way catalyst (LNT-TWC) or ammoxidation (AMOx).
The second aspect of the present invention is related to a kind of system.In the 14th embodiment, system includes first to the 13rd
The catalyst of embodiment and the lean-combustion engine swum over the catalyst.
In the 15th embodiment, the system for improving the 12nd embodiment, it further includes the second catalyst
With optional particulate filter.
In the 16th embodiment, the system for improving the 13rd embodiment, wherein the second catalyst is selected from triple effect
Catalyst (TWC), gasoline engine particulate filter (GPF), SCR (SCR), lean-burn NOxTrap (LNT), ammonia oxygen
Change (AMOx), SCR (SCRoF) on the filter and combinations thereof.
Brief description
Fig. 1 is can be comprising containing according to a honeycomb type fire resisting base members for the washcoat composition of the catalyst of embodiment
Perspective view；
Fig. 2 is the partial section amplified relative to Fig. 1 and intercepted along the plane parallel with the end face of the substrate of Fig. 1, its
The zoomed-in view of one of the gas flow shown in display Fig. 1；
Fig. 3 is when fresh and in N2In 2%O2With in 10% steam at 950 DEG C after aging 5 hours by according to reality
Apply the CeO that the XRD of example is measured2Crystallite granularity curve map；With
Fig. 4 is measured by the XRD according to embodiment after aging 8 hours at 850 DEG C in 10% steam/air
CeO2Crystallite granularity curve map.
Describe in detail
Before several exemplaries of the invention are described, it is to be understood that the invention is not restricted to description below
The construction of middle elaboration or the details of processing step.The present invention can have other embodiments and can be implemented and carried out in a variety of ways.
Embodiment of the invention, it has been found that, by barium component (such as BaCO3And/or BaO) it is incorporated to titanium dioxide
Cerium-aluminum oxide (CeO2/Al2O3) in CeO2There is provided with huge static stabilization and thus to have and improved than conventional art
Hydrothermal stability, NO higherxThe NO of trapping capacity and Geng GaoxThe catalyst material of conversion ratio.
In one or more embodiments, catalyst is comprising ceria-alumina particle and is supported on the dioxy
Change cerium-aluminium oxide particles on alkaline earth metal component, the ceria-alumina particle have by based on oxide about
The ceria phase that compound weight percentage in the range of 20% to about 80% is present.By the fresh and aging of XRD acquisitions
The average CeO of sample2Crystallite granularity can be used as CeO2Hydrothermal stability is measured.Correspondingly, in one or more embodiments
In, CeO2With hydrothermally stable and with N2In 2%O2It is less than after aging 5 hours at 950 DEG C with 10% steam
Average crystallite granularity microcrystalline form exist.
On term used in the disclosure, there is provided following definition.
Term " catalyst " used herein or " catalyst material " or " catalysis material " refer to the material for promoting reaction.
Term " layer " used herein and " layering " refer to be supported on surface, such as the structure in substrate.At one or many
In individual embodiment, catalyst of the invention is coated in substrate or base members as washcoat, with the forming layer in substrate.
Term " washcoat " used herein has its its ordinary meaning in the art, that is, be applied to sufficiently porous to permit
Perhaps the support base material that the gas streams for processing are passed through, such as the catalysis material on honeycomb type supporting member or other materials is thin
Adherent coating.As understood in this area, washcoat available from slurry form particle dispersion, slurry is applied in substrate, does
It is dry and calcine providing porous washcoat.
Term " carrier " used herein refer to carry thereon other chemical compounds or element in lower high surface
Material.Carrier particle have be more thanHole and distribution of pores wide.As defined herein, such metal oxide carrier is not
Including molecular sieve, especially zeolite.In specific embodiments, it is possible to use high surface refractory metal oxide carriers, example
Such as alumina supporting material, also referred to as " gamma-alumina " or " activated alumina ", it is typically exhibited more than 60 meters squared per grams
(“m2/ g "), typically up to about 200 meters squared per grams or BET surface area higher.Such activated alumina is typically oxidation
The mixture of the γ and δ phases of aluminium, but it is also possible to η, κ and θ the oxidation aluminium phase containing significant quantity.Can be using beyond activated alumina
Refractory metal oxides as at least some catalyst components in given catalyst carrier.For example, Bulk cerium oxide, oxygen
Change zirconium, alpha-aluminium oxide, silica, titanium dioxide and other materials and become known for this kind of purposes.
In one or more embodiments, catalyst includes ceria-alumina particle.Ceria-alumina
Particle has ceria phase, and ceria is by the catalyst weight based on oxide in the range of about 20% to about 80%
Amount percentage is present, including 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%
Or 80%.In one or more specific embodiments, the average CeO of the fresh and aged samples obtained by XRD2Crystallite granularity
Can be used as CeO2Hydrothermal stability is measured.Correspondingly, in one or more embodiments, CeO2With hydrothermally stable and have
In N2In 2%O2It is less than after aging 5 hours at 950 DEG C with 10% steamAverage crystallite granularity crystallite shape
Formula exist, the Average crystallite granularity include 160,155,150,140,130,120,110,10.0,90,80,70,60,50,
40th, 30,20,10 andIn a specific embodiment, ceria-alumina particle include by based on oxide
The ceria phase that compound weight percentage in the range of about 30% to 80 weight % is present.It is very specific real at one
Apply in scheme, ceria-alumina particle is included by the compound weight hundred of based on oxide about 50% to 80 weight %
Divide the ceria phase than existing.
In one or more embodiments, CeO2With hydrothermally stable and at 950 DEG C it is aging it is rear it is resistance to grow into it is bigger micro-
Brilliant microcrystalline form is present.It is no more than average that term " resistance to growth " used herein refers to that crystallite grows to after weatheringGranularity.In a specific embodiment, in catalytic article in 2%O2With 10% steam/N2In it is old at 950 DEG C
By the CeO of XRD determining after changing 5 hours2Crystallite granularity is less thanAccording to one or more embodiments, powder sample
With the CeO of the catalyst of coating2Crystallite granularity is different.In the catalyst of coating, other washcoated layer components can be to CeO2With steady
It is set for using.Therefore, after aging at same 950 DEG C, the CeO of the catalyst of the coating2Crystallite granularity is less than powder.
Term " Average crystallite granularity " used herein refers to the particle mean size such as by XRD determining as described below.
Term " XRD " used herein refers to X-ray diffraction crystallography, and it is the atomic and molecular structure for determining crystal
Method.In XRD, crystallization atom makes x- beams towards many specific direction diffraction.By the angle for measuring these diffracted beams
Degree and intensity, can produce the 3-D view of the electron density in crystal.By this electron density, it may be determined that the original in crystal
Sub- position, and their chemical bond, their out-of-sequence and other information.Especially, XRD can be used to estimate crystallite granularity；Peak
Width is inversely proportional with crystallite granularity；As crystallite granularity diminishes, peak broadens.In one or more embodiments, measured using XRD
CeO2The Average crystallite granularity of particle.
The width at XRD peaks is interpreted to size and strains the combination of all related broadening effect.It is given below for surveying
Both formula fixed.First equation is the crystallite granularity for full width at half maximum intensity FWHM information to be changed into given phase below
Scherrer equations.Second equation is used to (be considered as such as the 3rd equation by the overall width or amplitude at peak width information and peak
Shown in the two effects summation) calculate crystal in strain.It is noted that size and the broadening phase by different way of strain
Change for Bragg angle θ.The constant of Scherrer equations is discussed below.
βe=C ε tan θ
The constant of Scherrer equations is
K:Shape constant, we use 0.9 value
L:Peak width, it is by using NIST SRM 660b LaB6 Line Position＆Line Shape Standard
To correct the influence from instrumental optics
Θ:The 1/2 of 2 θ values of associated reflections
λ:Radiation wavelength
" crystallite granularity " used herein is not understood as coherent scattering domain perpendicular to that group of lattice plane for producing reflection
Length on direction.For CeO2, CeO2<111>Reflection is CeO2X-ray diffracting spectrum in highest peak.CeO2<111>
Atomic plane intersect with each crystallographic axis at unity and perpendicular to<111>The body diagonal that vector is represented.Therefore, by CeO2111 reflections
FWHM calculateCrystallite granularity be considered as substantially 100 layers<111>Atomic plane.
Different directions in crystal can produce different but close crystallite granularities with therefore reflection.Only it has been in crystal
These values are just accurate when U.S. spherical.Consider total peak width by size and strain effect solution using Williamson Hall curve negotiatings
Following linear equation is interpreted as, the slope of line represents strain, and intercept is crystal size.
In order to determine the crystallite granularity of material, single reflection or the FWHM values from complete X-ray diffracting spectrum are determined.
Single reflection is traditionally fitted to determine the FWHM values of the reflection, for the influence correction FWHM values from instrument, has then been made
The FWHM values of correction are converted into crystallite granularity with Scherrer equations.This passes through to ignore all from the strain in crystal
Effect is realized.This method is mainly used in ask relevant with the crystallite granularity of noble metal (we only have single available reflection to it)
Topic.It is noted that in peak is fitted, it is desirable to clean reflection not Chong Die with the reflection from other phases.Current is washcoated
The fact that being formulated few, currently uses Rietveld methods.Rietveld methods can use the known crystalline substance of the phase for existing
Body structure is fitted complete X-ray diffracting spectrum.Crystal structure serves as to the limitation of fit procedure or lock (brakes).For each
Phase, changes phase content, lattice parameter and FWHM information until whole Model Matching experimental data.
In the following embodiments, the lab diagram of fresh and aged samples is simulated using Rietveld methods.Using to each
Each FWHM curve determination crystallite granularities for mutually determining in sample.Do not include strain effect.
Term " alkaline-earth metal " used herein refers to one or more chemical element defined in the periodic table of elements, including
Beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) and radium (Ra).In one or more embodiments, alkaline-earth metal group
Dividing can be used as salt and/or sulfate and/or oxide (such as BaCO3、BaSO4And/or BaO) be incorporated in catalyst to provide " alkali
Earth metal component ".It is to be noted, that in calcining, barium component can change into barium carbonate and/or barium monoxide.In one or more implementations
In scheme, alkaline earth metal component includes barium component.Alkaline earth metal component can be by based on oxide about 0.5 weights of weight % to 50
Amount %, including 0.5,1,2,3,4,5,10,15,20,25,30,35,40,45 and 50% amount is present in washcoat.At one
In specific embodiment, alkaline earth metal component is included and deposited by the amount of based on the oxide about 0.5 weight % of weight % to about 50
Barium component.In other specific embodiments, alkaline earth metal component is included by based on oxide about 5 weight % to big
The barium component that the amount of about 30 weight % is present.
In one or more embodiments, the CeO of the aged samples obtained by XRD is used2Crystallite granularity as alkaline earth/
Ce/Al hydrothermal stabilities are measured.
In a particular embodiment, when ceria-alumina particle barium precursor, particularly water-soluble barium precursor salt
(such as barium acetate) (precursor salt provides barium carbonate (BaCO through calcining3) and/or barium monoxide (BaO)) dipping when, it was observed that huge
Static stabilization.Reference picture 3, in N2In 2%O2With in 10% steam at 950 DEG C after aging 5 hours, BaCO3/
(CeO2-Al2O3) sample CeO2Crystallite granularity is about 75 to aboutIt is interior.This is significantly lower than aging BaCO3/CeO2
Powder ().In 70%CeO2/Al2O3Apply other BaCO on powder3Carrying capacity is determining whether they can also carry
For similar effect.Reference picture 4, in 10% steam/air at 850 DEG C after aging 8 hours, is loaded with 15,10 and 5 weight % barium
The sample of component (being calculated with barium monoxide) shows to compare BaCO3/CeO2Much lower CeO2Crystallite granularity.In general, barium component
(such as BaCO3And/or BaO) seem there is unique stabilization to be turned into the ceric oxide crystallite growth in Ba/Ce/Al systems
With.This static stabilization also benefits to the NO in such as LNT catalystxTrapping.From smaller crystallite granularity extra two
Cerium oxide surface area realizes more low temperature ceria base NOxTrapping, improvement WGS and improvement PGM dispersions.
Therefore, according to one or more embodiments, ceria unstability in Ba-Ce systems is determined, and in Ba-Ce-Al
Significantly stabilized in system.
In one or more embodiments, it is not intended to be subject to theory, it is believed that from smaller crystallite granularity extra two
Cerium oxide surface area realizes BaCO higher3Base NOxTrapping (is attributed to more preferable BaCO3Dispersion), it is higher at low temperature
CeO2Base NOxTrapping, improved NOxReduction (being attributed to more effective WGS) and improved NO oxidations and NOxReduction (is attributed to more
Good PGM dispersions).Therefore, by barium (BaCO3And/or BaO) it is incorporated to ceria-alumina (CeO2/Al2O3) in CeO2Tool
Having huge static stabilization and providing has hydrothermal stability more improved than conventional art, NO higherxTrapping capacity and more
NO highxThe catalyst material of conversion ratio.
In one or more embodiments, in 2%O2With 10% steam/N2In at 950 DEG C after aging 5 hours, this hair
Bright catalyst shows the improved NO in lean-burn runningxTrapping capacity and the improved NO in fuel-rich regenerative processxAlso
It is former.The improvement be relative to comprising not with Al2O3With reference to ceria traditional catalyst.
In one or more embodiments, catalyst of the invention can be used as three-way catalyst (TWC), oxidative diesel
Catalyst (DOC), gasoline engine particulate filter (GPF), lean-burn NOxTrap (LNT), integrated LNT-TWC or as ammoxidation
Catalyst (AMOx).
In one or more embodiments, catalyst is further included and is supported on barium (ceria-alumina) particle
On at least one platinum group metal.Term " platinum group metal " used herein or " PGM " refer to defined in the periodic table of elements
Plant or various chemical elements, including platinum, palladium, rhodium, osmium, iridium and ruthenium and its mixture.In one or more embodiments, platinum family
Metal is selected from platinum, palladium, rhodium, iridium and its mixture.In a specific embodiment, platinum group metal is selected from platinum, palladium, rhodium and its mixes
Compound.Generally, the total platinum group metal content to involved catalyst is not specifically limited.
Generally, catalyst of the invention is arranged in substrate.Substrate can be commonly used for preparing those materials of catalyst
Any materials of material, generally comprise ceramics or metal honeycomb structure.Any suitable substrate can be used, such as has to enter from substrate
The monolith substrates of the type of mouth or exit face thin parallel gas flow channels therethrough, so that passage is opened flowing through fluid therein
Put (herein referred to as flow through substrate).The essentially straight path of fluid issuing from their fluid intake to them
Passage delimited by wall, catalysis material be coated on wall as washcoat so that the gas for flowing through passage contacts the catalysis material.
The runner of monolith substrates is thin-walled channels, its can have any suitable section shape and size, such as trapezoidal, rectangle, square,
Sine curve, hexagon, ellipse, circle etc..
Such monolith substrates can contain up to about 900 or more runner (or " hole ")/square inch sections, although
Much less amount can be used.For example, substrate may have about 7 to 600, more typically about 100 to 400 holes/square
Inch (" cpsi ").Hole can be with rectangle, square, circle, ellipse, triangle, hexagon or other polygonal section
Face.Ceramic bases can be by any suitable refractory material, such as cordierite, cordierite-aluminum oxide, silicon nitride or carborundum system
Into, or the substrate can be made up of one or more metal or metal alloy.
The catalyst of embodiment of the invention can be applied to substrate table by any any means known in this area
On face.For example, catalyst wash coat can be by spraying, powder coated or brushing or by surface impregnation to the carbon monoxide-olefin polymeric
Apply.
In one or more embodiments, catalyst is arranged in honeycomb substrates.
When applying as washcoat, the present invention is easier to understand with reference to Fig. 1 and 2.Figures 1 and 2 show that of the invention
One fire resisting base members 2 of embodiment.Reference picture 1, fire resisting substrate unit 2 is with cylindrical outer surface 4, the and of upstream face 6
With the cylinder of the identical downstream end face 8 of end face 6.Base members 2 have the thin parallel gas flow channels 10 of the multiple for being formed wherein.
As found out in Fig. 2, runner 10 is formed and from upstream face 6 to downstream end face 8 through substrate by wall 12, and passage 10 is unobstructed with permission
Fluid, such as gas material flow longitudinally through substrate via gas channel 10.(it is in the art and under for single catalyst layer 14
Adhere in text sometimes referred to as " washcoat ") or be applied on the wall 12 of base members.In some embodiments, in catalyst
Additional catalyst oxidant layer 16 is coated with layer 14.Second catalyst layer 16 can be constituted with the identical of catalyst layer 14, or second urges
Agent layer 16 can include different carbon monoxide-olefin polymerics.
As shown in Figure 2, base members include the void space that is provided by gas channel 10, and these passages 10 section
The thickness of area and the wall 12 for delimiting passage becomes with the type of base members.Similarly, it is applied to washcoated in such substrate
The weight of layer optionally becomes.Therefore, when the amount of other components of washcoat or catalytic metal component or said composition is described,
The use of the unit of the composition weight based on per unit volume substrate is convenient.Therefore, unit of gram/cubic feet per used herein
Very little (" g/in3") and gram/cubic feet (" g/ft3") represent every volume base members (including the void space of base members
Volume) composition weight.
In the second aspect of the invention, the catalyst of one or more of embodiments can be used in comprising one
Or in multiple integrated discharge treating systems for the additional components for processing exhaust emission.For example, discharge treating system
Can be included in the lean-combustion engine of the catalyst upstream of one or more embodiments, and can further include the second catalyst and
Optionally include particulate filter.In one or more embodiments, the second catalyst is selected from three-way catalyst (TWC), gasoline
Machine particulate filter (GPF), SCR (SCR), lean-burn NOxTrap (LNT), ammoxidation (AMOx), filtering
SCR (SCRoF) on device and combinations thereof.In one or more embodiments, particulate filter may be selected from gasoline engine particulate mistake
Filter, soot filter or SCRoF.Particulate filter can be catalyzed for specific function.Catalyst can be located at particulate filter
Upstream or downstream.
In one or more embodiments, discharge treating system can be included in the catalyst of one or more embodiments
The lean-combustion engine of upstream, and can further include TWC.In one or more embodiments, discharge treating system can enter one
Step includes SCR/LNT.
In a specific embodiment, particulate filter is the soot filter (CSF) of catalysis.CSF can be included with containing
There is the base of the washcoat coating of one or more catalyst for the soot and/or oxidation exhaust stream emission of burn off trapping
Bottom.In general, soot burnt catalyst can be any known catalysts for soot burnt.For example, CSF can use one
Plant or various high surface refractory oxides (such as aluminum oxide, silica, silica alumina, zirconium oxide and zirconium oxide
Aluminum oxide) and/or oxidation catalyst (such as ceria-zirconia) coating for burning unburned hydrocarbon and to a certain extent
Burning particles thing.In one or more embodiments, soot burnt catalyst is urged comprising one or more noble metal (PM)
The oxidation catalyst of agent (platinum, palladium and/or rhodium).
In general, it is possible to use any known filter substrate in this area, including such as honeycomb wall flow filters
Device, winding or fiberfill fibers filter, open celled foam, sintered metal filter etc., are specifically exemplified by wall-flow filter.Can be used for
The wall-flow type substrate of load C SF compositions has the multiple thin substantially parallel gas channel extended along the longitudinal axis of substrate.It is logical
Often, each passage is closed in one end of base body, with the alternate channel closed in opposite end face.Such monolith substrates can contain
Up to about 900 or more runner (or " hole ")/square inch sections, although much less amount can be used.For example,
Substrate may have about 7 to 600, more typically about 100 to 400 hole/square inches (" cpsi ").Embodiment party of the invention
Porous flow honeycomb filter used has a high regard for choosing to be catalyzed in case, i.e., the wall of described element have thereon or its be contained within it is a kind of or
Various catalysis materials, described above is such CSF carbon monoxide-olefin polymerics.Catalysis material may be present in the only entrance of element wall
On side, only outlet side, entrance and exit side, or wall can be made up of catalysis material wholly or in part in itself.In another embodiment party
In case, the present invention may include to use one or more catalysis material washcoats and one on the entrance and/or exit wall of the element
The combination of individual or multiple catalysis material washcoats.
The present invention is described referring now to the following example.Before several exemplaries of the invention are described,
Understand, the invention is not restricted to the construction or the details of processing step that are proposed in description below.The present invention can have other to implement
Scheme and can be implemented and carried out in a variety of ways.
Embodiment
The preparation of 1-catalyst of embodiment
CeO2-Al2O3Particle (1A to 5A) is impregnated to provide sample 1B to 5B with barium acetate solution, and they have as in table 1
Specified BaCO3/(CeO2-Al2O3) and BaCO3Content.The mixture dried at 110 DEG C and at 720 DEG C calcining it is 2 small
When.
CeO2-Al2O3Particle (4A) is impregnated to provide 4C to 4E with barium acetate solution, and they have as indicated in table 1
BaCO3/(CeO2-Al2O3) and BaCO3Content.The mixture is dried at 110 DEG C and calcined 2 hours at 620 DEG C.
CeO2Particle (6A) is impregnated to provide 6B and 6C with barium acetate solution, and they have the BaCO as indicated in table 13/
CeO2And BaCO3Content.The mixture is dried at 110 DEG C and calcined 2 hours at 600 DEG C.
Reference picture 3, in N2In 2%O2With in 10% steam at 950 DEG C after aging 5 hours, BaCO3/(CeO2-
Al2O3) sample 1B-5B CeO2Crystallite granularity 79 toIt is interior.
Reference picture 4, in atmosphere in 10% steam at 850 DEG C after aging 8 hours, BaCO3/(CeO2-Al2O3) sample
The CeO of 4C to 4E2Crystallite granularity 73 toIt is interior.
The display of table 1 1A to 6A and 1B to 6B, 6C, the content of 4C to 4E.
Table 1
* aging condition:In N2In 2%O2With in 10% steam aging 5 hours at 950 DEG C
- the XRD of embodiment 2 is measured
The CeO of the sample of embodiment 1 is measured by XRD2Crystallite granularity.Use mortar and pestle sample.Gained powder
Then it is backfilling into flat base (flat plate mounts) for analysis.Use θ-θ PANalytical X ' Pert Pro
MPD X-ray diffractions system collects data in Bragg-Brentano geometry.Light path is by X-ray pipe, 0.04rad
Soller slits, 1/4 ° of divergent slit, 15mm light beam masks, 1/2 ° of antiscatter slits, sample, 1/4 ° of antiscatter slits,
0.04rad soller slits, Ni ° of optical filter and with 2.114 ° of PIXcel linear position sensitive detector structures of effective length
Into.In this analysis Cu is used in the case where the generator of 45kV and 40mA is setkαRadiation.Walk using 0.026 ° of stride and often 600s
Gate time from 10 ° to 90 ° 2 θ collect X-ray diffraction data.The identification of phase is carried out using Jade softwares.All numerical value make
Determined with Rietveld methods.
This specification mentions " embodiment ", " some embodiments ", " one or more embodiments " in the whole text
Or " embodiment " refer to the specific factor of embodiment description, structure, material or feature are included in it is of the invention
In at least one embodiment.Therefore, as " in one or more embodiments ", " in certain embodiments ", " at one
In embodiment " or this specification appearance in the whole text everywhere that is expressed in of " in one embodiment " etc be not necessarily referring to this hair
Bright same embodiment.Additionally, specific factor, structure, material or feature can be combined at one in any suitable manner
Or in multiple embodiments.The description order of the above method is not construed as limitation, and method can using disengaging order or
With deleting or the increased operation.
It is to be understood that description above mean it is exemplary and nonrestrictive.Many other embodiments are in this area
Those of ordinary skill is readily apparent that after reading description above.Therefore, appended claims and these claims be should refer to
The full breadth of equivalent determine the scope of the present invention.
Claims (15)
1. a kind of catalyst, it is included
Dioxy with the ceria phase existed by the particle weight percentage of about 20% to about 80% based on oxide
Change cerium-aluminium oxide particles, the alkaline earth metal component being supported on the ceria-alumina particle, wherein CeO2With hydro-thermal
Stablize and with N2In 2%O2It is less than after aging 5 hours at 950 DEG C with 10% steamAverage crystallite
The microcrystalline form of degree is present.
2. the catalyst of claim 1, wherein the alkaline earth metal component includes barium component.
3. the catalyst of claim 2, wherein the barium component is selected from barium monoxide and barium carbonate.
4. the catalyst of any one of claim 1-3, wherein the ceria-alumina particle is ceria and aluminum oxide
Compound.
5. the catalyst of any one of claim 1-4, it is further comprising being supported on the ceria-alumina particle
Selected from least one platinum group metal of platinum, palladium, rhodium, iridium and its mixture.
6. the catalyst of claim 5, wherein the platinum group metal is selected from platinum, palladium, rhodium and its mixture.
7. the catalyst of claim 2, wherein the barium component is by the amount of based on oxide about 0.5 weight of weight % to 50 %
In the presence of especially the barium component exists by the amount of based on oxide about 5 weight of weight % to 30 %.
8. the catalyst of claim 4, wherein CeO2And Al2O3Compound contain about 30 to the 80 weight % based on oxide
Amount ceria.
9. the catalyst of claim 4, wherein CeO2And Al2O3Compound contain about 50 to the 80 weight % based on oxide
Amount ceria.
10. the catalyst of claim 5 or 6, wherein the platinum group metal is made up of platinum and palladium substantially.
The catalyst of 11. claims 5 or 6, wherein the platinum group metal is made up of platinum substantially.
The catalyst of 12. claim any one of 1-11, wherein the catalyst is selected from three-way catalyst (TWC), diesel engine oxygen
Change catalyst (DOC), gasoline engine particulate filter (GPF), lean-burn NOxTrap (LNT), integrated lean-burn NOxTrap-triple effect
Catalyst (LNT-TWC) or ammoxidation (AMOX).
A kind of 13. systems, its catalyst for including claim any one of 1-12 and the lean-burn swum over the catalyst start
Machine.
The system of 14. claims 13, it further includes the second catalyst and optional particulate filter.
The system of 15. claims 14, wherein the second catalyst is selected from three-way catalyst (TWC), gasoline engine particulate filter
(GPF), SCR (SCR), lean-burn NOxTrap (LNT), ammoxidation (AMOx), SCR on the filter
(SCRoF) and combinations thereof.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14/467,250 | 2014-08-25 | ||
| US14/467,250 US9611774B2 (en) | 2013-03-13 | 2014-08-25 | Catalyst with improved hydrothermal stability |
| PCT/US2015/046695 WO2016033046A1 (en) | 2014-08-25 | 2015-08-25 | Catalyst with improved hydrothermal stability |
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| Publication Number | Publication Date |
|---|---|
| CN106794447A true CN106794447A (en) | 2017-05-31 |
Family
ID=55400431
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|---|---|---|---|
| CN201580045670.8A Pending CN106794447A (en) | 2014-08-25 | 2015-08-25 | Catalyst with improved hydrothermal stability |
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| Country | Link |
|---|---|
| EP (1) | EP3186003A4 (en) |
| JP (1) | JP6785755B2 (en) |
| KR (1) | KR102369734B1 (en) |
| CN (1) | CN106794447A (en) |
| BR (1) | BR112017002085A2 (en) |
| CA (1) | CA2955817C (en) |
| MX (1) | MX2017002502A (en) |
| WO (1) | WO2016033046A1 (en) |
| ZA (1) | ZA201701901B (en) |
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| WO2019042911A1 (en) * | 2017-08-29 | 2019-03-07 | Rhodia Operations | Use of a mixed oxide to absorb nox |
| KR20200124270A (en) * | 2018-02-26 | 2020-11-02 | 바스프 코포레이션 | Gasoline engine exhaust gas post-treatment catalyst |
| JP7443370B2 (en) | 2018-08-24 | 2024-03-05 | ローディア オペレーションズ | Microporous aluminotitanosilicate crystalline zeolite, its preparation method and use |
| CN114728234A (en) * | 2019-11-12 | 2022-07-08 | 巴斯夫公司 | Particulate filter |
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| US4965243A (en) * | 1987-08-28 | 1990-10-23 | Engelhard Corporation | Process for producing a catalyst for purifying exhaust gases from internal combustion engines |
| US5075275A (en) * | 1989-07-06 | 1991-12-24 | Mazda Motor Corporation | Catalyst for purification of exhaust gases |
| US6296822B1 (en) * | 2000-03-29 | 2001-10-02 | Ford Global Technologies, Inc | Process for manufacturing nox traps with improved sulfur tolerance |
| US20080120970A1 (en) * | 2006-11-29 | 2008-05-29 | Marcus Hilgendorff | NOx Storage Materials and Traps Resistant to Thermal Aging |
| CN105188920A (en) * | 2013-03-13 | 2015-12-23 | 巴斯夫公司 | NOx storage catalyst with improved hydrothermal stability and NOx conversion |
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|---|---|---|---|---|
| US5064803A (en) * | 1990-08-31 | 1991-11-12 | Allied-Signal Inc. | Preparation of three-way catalysts with highly dispersed ceria |
| US6348430B1 (en) * | 1997-06-20 | 2002-02-19 | Degussa Ag | Exhaust gas treatment catalyst for internal combustion engines with two catalytically active layers on a carrier structure |
| US6221804B1 (en) * | 1998-01-27 | 2001-04-24 | Mazda Motor Corporation | Catalyst for purifying exhaust gas and manufacturing method thereof |
| ES2522965T3 (en) * | 2008-07-31 | 2014-11-19 | Basf Se | NOx storage materials and thermal aging resistant traps |
| JP5768474B2 (en) * | 2011-04-28 | 2015-08-26 | 日産自動車株式会社 | Exhaust gas purification system |
| JP5806131B2 (en) * | 2012-01-20 | 2015-11-10 | エヌ・イーケムキャット株式会社 | NOx storage denitration catalyst |
-
2015
- 2015-08-25 WO PCT/US2015/046695 patent/WO2016033046A1/en active Application Filing
- 2015-08-25 BR BR112017002085A patent/BR112017002085A2/en not_active IP Right Cessation
- 2015-08-25 JP JP2017511323A patent/JP6785755B2/en active Active
- 2015-08-25 EP EP15835062.9A patent/EP3186003A4/en active Pending
- 2015-08-25 KR KR1020177004943A patent/KR102369734B1/en active IP Right Grant
- 2015-08-25 CA CA2955817A patent/CA2955817C/en active Active
- 2015-08-25 CN CN201580045670.8A patent/CN106794447A/en active Pending
- 2015-08-25 MX MX2017002502A patent/MX2017002502A/en unknown
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2017
- 2017-03-17 ZA ZA2017/01901A patent/ZA201701901B/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4965243A (en) * | 1987-08-28 | 1990-10-23 | Engelhard Corporation | Process for producing a catalyst for purifying exhaust gases from internal combustion engines |
| US5075275A (en) * | 1989-07-06 | 1991-12-24 | Mazda Motor Corporation | Catalyst for purification of exhaust gases |
| US6296822B1 (en) * | 2000-03-29 | 2001-10-02 | Ford Global Technologies, Inc | Process for manufacturing nox traps with improved sulfur tolerance |
| US20080120970A1 (en) * | 2006-11-29 | 2008-05-29 | Marcus Hilgendorff | NOx Storage Materials and Traps Resistant to Thermal Aging |
| CN105188920A (en) * | 2013-03-13 | 2015-12-23 | 巴斯夫公司 | NOx storage catalyst with improved hydrothermal stability and NOx conversion |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2955817C (en) | 2023-09-26 |
| MX2017002502A (en) | 2017-05-23 |
| ZA201701901B (en) | 2021-06-30 |
| CA2955817A1 (en) | 2016-03-03 |
| EP3186003A1 (en) | 2017-07-05 |
| KR20170047239A (en) | 2017-05-04 |
| EP3186003A4 (en) | 2017-08-30 |
| WO2016033046A1 (en) | 2016-03-03 |
| KR102369734B1 (en) | 2022-03-04 |
| JP2017530859A (en) | 2017-10-19 |
| BR112017002085A2 (en) | 2018-01-30 |
| JP6785755B2 (en) | 2020-11-18 |
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