WO2017134065A1 - Mehrschichtiger stickoxidspeicherkatalysator mit mangan - Google Patents
Mehrschichtiger stickoxidspeicherkatalysator mit mangan Download PDFInfo
- Publication number
- WO2017134065A1 WO2017134065A1 PCT/EP2017/052081 EP2017052081W WO2017134065A1 WO 2017134065 A1 WO2017134065 A1 WO 2017134065A1 EP 2017052081 W EP2017052081 W EP 2017052081W WO 2017134065 A1 WO2017134065 A1 WO 2017134065A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oxide
- storage catalyst
- washcoat
- catalyst according
- nitrogen
- Prior art date
Links
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 239000011572 manganese Substances 0.000 title description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title description 5
- 229910052748 manganese Inorganic materials 0.000 title description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 58
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 54
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 46
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 32
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 22
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 19
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000010948 rhodium Substances 0.000 claims description 15
- 229910052703 rhodium Inorganic materials 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 12
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 11
- 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
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 230000018537 nitric oxide storage Effects 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 abstract 1
- 229910003445 palladium oxide Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000011068 loading method Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000011232 storage material Substances 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000011656 manganese carbonate Substances 0.000 description 5
- 229940093474 manganese carbonate Drugs 0.000 description 5
- 235000006748 manganese carbonate Nutrition 0.000 description 5
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 5
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 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
- 239000007791 liquid phase Substances 0.000 description 2
- 150000002697 manganese compounds Chemical class 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- -1 platinum group metals Chemical class 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001294 propane Substances 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
Classifications
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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
- F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
- F01N3/0814—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents combined with catalytic converters, e.g. NOx absorption/storage reduction catalysts
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- 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
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
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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
- B01D53/9404—Removing only nitrogen compounds
- 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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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
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- B01J35/19—Catalysts containing parts with different compositions
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- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
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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
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- F01N3/0828—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents characterised by the absorbed or adsorbed substances
- F01N3/0842—Nitrogen oxides
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- F01N2370/00—Selection of materials for exhaust purification
- F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
-
- 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
- F01N2510/00—Surface coverings
- F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
- F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
- F01N2510/0684—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having more than one coating layer, e.g. multi-layered coatings
Definitions
- the present invention relates to a catalyst for the reduction of nitrogen oxides, which is contained in the exhaust lean burned internal combustion engines.
- nitrogen oxide storage catalysts for which the term “lean NOx trap” or "LNT” is common known.
- Their cleaning effect is based on the fact that in a lean phase of operation of the engine, the nitrogen oxides are stored by the storage material of the storage catalyst mainly in the form of nitrates and decomposed in a subsequent rich phase of operation of the engine again and released so the nitrogen oxides with the reducing
- Suitable storage materials are, in particular, oxides, carbonates or hydroxides of magnesium, calcium, strontium, barium, the alkali metals, the rare earth metals or mixtures thereof. Due to their basic properties, these compounds are capable of forming nitrates with the acidic nitrogen oxides of the exhaust gas and of storing them in this way. They are suitable for generating a large interaction area with the exhaust gas in the highest possible dispersion
- nitrogen oxide storage catalysts generally contain noble metals such as platinum, palladium and / or rhodium as catalytically active components. Their task is, on the one hand, to oxidise NO to NO 2, CO and HC to CO 2 under lean conditions and, on the other hand, to reduce released NO 2 to nitrogen during the rich operating phases in which the nitrogen oxide storage catalyst is regenerated.
- EP 0 885 650 A2 describes an exhaust gas purification catalyst for internal combustion engines with two catalytically active layers on a support body.
- the layer directly on the support body comprises one or more highly dispersed alkaline earth oxides, at least one
- Platinum group metal as well as at least one finely divided, oxygen-storing material.
- the platinum group metals are in close contact with all components of the first layer.
- the second layer is in direct contact with the exhaust gas and contains at least one platinum group metal and at least one finely divided oxygen storing material. Only part of the finely divided solids of the second layer serve as a carrier for the platinum group metals.
- the catalyst is a three-way catalytic converter that controls the harmful components of the exhaust gas
- a nitrogen oxide storage catalyst which comprises two superimposed catalyst layers on a carrier substrate.
- the lower layer lying directly on the carrier substrate comprises one or more noble metals, as well as one or more nitrogen oxide storage components.
- the upper layer comprises one or more
- Precious metals, as well as cerium oxide and is free of alkali or alkaline earth components Catalyst substrates containing nitrogen oxide storage materials and having two or more layers are also described in WO 2012/029050.
- the first layer is directly on the carrier substrate and comprises platinum and / or palladium, while the second layer is on the first and comprises platinum.
- Both layers also contain one or more oxygen storage materials and one or more nitric oxide storage materials comprising one or more alkali and / or alkaline earth metals.
- the total amount of alkali and alkaline earth metal in the nitrogen oxide storage materials is 0.18 to 2.5 g / in 3 , calculated as alkali metal oxide M2O and alkaline earth metal oxide MO.
- manganese compounds in particular manganese oxide
- DE102011109200A1 and US2015 / 165422 describe manganese-containing diesel oxidation catalysts.
- DE102012204524A1 describes LNT catalysts which contain manganese-containing mixed oxides, for example MnOx-CeO 2 .
- US2013 / 336865 also describes NOx absorber catalysts which may contain manganese.
- the present invention relates to a nitrogen oxide storage catalyst comprising at least two catalytically active washcoat layers on one
- cerium oxide as well as platinum and palladium and is free of alkali and alkaline earth compounds.
- the cerium oxide used in washcoat layers A and B can be any cerium oxide used in washcoat layers A and B.
- cerium oxide is used in the washcoat layer A in an amount of from 110 to 160 g / l, for example from 125 to 145 g / l.
- cerium oxide is used in amounts of 22 to 120 g / l, for example 40 to 100 g / l or 45 to 65 g / l.
- Suitable alkaline earth compounds in the washcoat A are, in particular, oxides, carbonates and / or hydroxides of magnesium, strontium and / or barium, in particular magnesium oxide, barium oxide and strontium oxide.
- Suitable alkali compounds in the washcoat A are, in particular, oxides, carbonates and / or hydroxides of lithium, potassium and / or sodium.
- the alkaline earth or alkali compound in washcoat A is present in amounts of 10 to 50 g / l, especially 15 to 20 g / l, calculated as alkaline earth oxide and based on the volume of the support body.
- manganese oxide in washcoat A is present in amounts of from 1 to 10 weight percent, preferably 2.5 to 7.5 Wt .-%, based on the sum of Washcoattiken A and B, each calculated as MnO before.
- the washcoat layer B also contains
- Washcoat layer B at up to 2.5 wt .-%, preferably 0.5 to 2.5 wt .-%, based on the sum of Washcoat füren A and B.
- manganese oxide is not used as a carrier material, neither for the noble metals platinum, palladium and optionally rhodium, nor for another component of washcoat A and optionally washcoat B.
- manganese oxide in the context of the present invention means in particular MnO, MnCh or Mn 2 O 3 or combinations of MnO 2 , MnO
- manganese oxide is not in the form of mixed oxides with other oxides of washcoat A and B layers.
- manganese oxide is not present in the form of a mixed oxide with cerium oxide, for example not in the form of MnOx-CeO 2 , MnO-ZrO 2 and
- the ratio platinum to palladium in the washcoat A in embodiments of the present invention is for example 4: 1 to 18: 1 or 6: 1 to 16: 1, for example 8: 1, 10: 1, 12: 1 or 14: 1.
- the ratio platinum to palladium in the washcoat layer B is also in embodiments of the present invention, for example 4: 1 to 18: 1 or 6: 1 to 16: 1, for example 8: 1, 10: 1, 12: 1 or 14: 1 but independent of the ratio in washcoat A
- washcoat B contains rhodium as another precious metal. Rhodium is in this case
- the total amount of noble metal i. of platinum, palladium and
- optionally rhodium, in the nitrogen oxide storage catalyst according to the invention is in embodiments of the present invention, 2.12 to 7.1 g / l (60 to 200 g / ft 3 ), based on the volume of the support body.
- the noble metals are platinum and palladium and optionally rhodium
- alumina silica
- titanium dioxide but also mixed oxides such as aluminum-silicon mixed oxides and cerium-zirconium mixed oxides.
- platinum and palladium and, optionally, rhodium are used as support material for the noble metals
- Alumina is used, in particular those which is stabilized by 1 to 6 wt .-%, in particular 4 wt .-%, lanthanum oxide.
- Manganese oxide preferably does not serve as a support for platinum and palladium and optionally rhodium.
- the total washcoat load of the support body is in
- Embodiments of the present invention 300 to 600 g / l, based on the volume of the support body.
- the present invention relates to a nitrogen oxide storage catalyst comprising at least two catalytically active washcoat layers on a support body,
- o cerium oxide in an amount of 100 to 160 g / l
- o contains manganese oxide in an amount of 10 to 20 g / l and
- washcoat caring A in amounts of 250 to 350 g / l and the Washcoat caring B in amounts of 80 to 130 g / l is present and wherein the amount g / l each refers to the volume of the support body.
- thermal aftertreatment (calcination and optionally reduction with forming gas or hydrogen). These methods are well known in the art.
- the necessary coating suspensions can after the
- the nitrogen oxide storage catalysts according to the invention are outstandingly suitable for converting NOx into exhaust gases of
- the nitrogen oxide storage catalysts according to the invention are thus suitable for Euro 6 applications.
- the present invention thus also relates to a method for
- Figure 1 NOx conversion of the catalysts Kl (dashed line) and VK1 (solid line) as a function of temperature.
- Figure 2 NOx conversion of the catalysts K2 (solid line) and K3 (dashed) as a function of temperature.
- Figure 3 NOx conversion of the catalysts K2 (solid line) and K4 (dashed) as a function of temperature.
- the loading of Pt and Pd is 35 g / ft 3 (1.236 g / l) and 3.5 g / ft 3 (0.124 g / l) and the total loading of the washcoat layer about 293 g / l based on the volume of the ceramic - Carrier.
- a further washcoat layer B is applied to the first washcoat layer, also containing Pt and Pd supported on alumina, and Rh supported on a lanthanum stabilized alumina.
- the loading of Pt, Pd and Rh in this washcoat layer is 35 g / ft 3 (1.236 g / l), 3.5 g / ft 3 (0.124 g / l) and 5 g / ft 3 (0.177 g / l).
- the washcoat layer B also contains 55 g / l of cerium oxide with a layer B washcoat loading of about 81 g / l.
- the catalyst thus obtained is hereinafter called Kl.
- Example 1 was repeated with the difference that washcoat A did not contain manganese oxide.
- the catalyst thus obtained is hereinafter called VK1.
- Atmosphere aged b) The NOx conversion of Kl or VK1 as a function of the temperature before the catalyst was determined in a model gas reactor in the so-called NOx conversion test.
- Hydrocarbon mixture (consisting of 33 ppm propene and 17 ppm propane) and a residual oxygen content of 7 vol .-% at one
- FIG. 1 shows the NO x conversions of the inventive catalyst K 1 and of the comparative catalyst VK 1 thus determined.
- the turnover of Kl in the entire temperature range is higher than the sales of VK1.
- a honeycomb ceramic support is coated with a first washcoat A, the Pt and Pd supported on alumina, ceria in an amount of 125 g / l, 21 g / l barium oxide, 7.5 g / l magnesium oxide and 7.5 g / l manganese oxide in the form of manganese carbonate.
- the loading of Pt and Pd is 35 g / ft 3 (1.236 g / l) and 3.5 g / ft 3 (0.124 g / l) and the
- Total loading of the washcoat layer about 299 g / l based on the volume of the ceramic carrier.
- another washcoat layer B is applied, which also contains Pt and Pd, and Rh supported on alumina.
- the loading of Pt, Pd and Rh in this washcoat layer is 35 g / ft 3 (1.236 g / l), 3.5 g / ft 3 (0.124 g / l) and 5 g / ft 3 (0.177 g / l).
- Washcoat layer B also contains 55 g / l of cerium oxide at one
- the catalyst thus obtained is hereinafter called K2.
- Example 2 was repeated with the difference that washcoat B additionally contained 2.5 g / l of manganese oxide in the form of manganese carbonate.
- the catalyst thus obtained is hereinafter called K3.
- Example 2 was repeated with the difference that washcoat A contained 15 g / l of manganese oxide in the form of manganese carbonate.
- the catalyst thus obtained is hereinafter called K4.
- Example 1 was repeated with the difference that the amounts of cerium oxide and manganese oxide indicated in Table 1 below were used.
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP17705036.6A EP3411143A1 (de) | 2016-02-02 | 2017-02-01 | Mehrschichtiger stickoxidspeicherkatalysator mit mangan |
US16/074,164 US20200032687A1 (en) | 2016-02-02 | 2017-02-01 | Multi-layer nitrogen oxide storage catalyst with manganese |
KR1020187025335A KR20180111903A (ko) | 2016-02-02 | 2017-02-01 | 망간을 함유하는 다층 질소 산화물 저장 촉매 |
CN201780009139.4A CN108602051A (zh) | 2016-02-02 | 2017-02-01 | 具有锰的多层氮氧化物储存催化剂 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102016101761.2A DE102016101761A1 (de) | 2016-02-02 | 2016-02-02 | Katalysator zur Reduktion von Stickoxiden |
DE102016101761.2 | 2016-02-02 |
Publications (1)
Publication Number | Publication Date |
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WO2017134065A1 true WO2017134065A1 (de) | 2017-08-10 |
Family
ID=58044022
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2017/052081 WO2017134065A1 (de) | 2016-02-02 | 2017-02-01 | Mehrschichtiger stickoxidspeicherkatalysator mit mangan |
Country Status (6)
Country | Link |
---|---|
US (1) | US20200032687A1 (de) |
EP (1) | EP3411143A1 (de) |
KR (1) | KR20180111903A (de) |
CN (1) | CN108602051A (de) |
DE (1) | DE102016101761A1 (de) |
WO (1) | WO2017134065A1 (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3623047A1 (de) | 2018-09-17 | 2020-03-18 | Umicore Ag & Co. Kg | Katalysator zur reduktion von stickoxiden |
EP3695902A1 (de) | 2019-02-18 | 2020-08-19 | Umicore Ag & Co. Kg | Katalysator zur reduktion von stickoxiden |
US11291976B2 (en) | 2019-10-18 | 2022-04-05 | Carus Llc | Mixed valent manganese-based NOx adsorber |
EP3592458B1 (de) * | 2017-03-06 | 2023-06-21 | Umicore AG & Co. KG | Mangan-haltiger dieseloxidationskatalysator |
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JP2022503617A (ja) * | 2018-08-27 | 2022-01-12 | ビーエーエスエフ コーポレーション | 卑金属をドープした酸化ジルコニウム触媒担体材料 |
KR102211944B1 (ko) * | 2019-04-04 | 2021-02-03 | 희성촉매 주식회사 | 귀금속 박층을 최상층으로 포함하는 다층구조의 배기가스 정화용 촉매 및 이의 제조방법 |
CN111821805B (zh) * | 2020-07-08 | 2021-08-20 | 昆明理工大学 | 一种软锰矿与含硫烟气资源化处理工艺 |
CN115634687A (zh) * | 2021-07-19 | 2023-01-24 | 上海歌地催化剂有限公司 | 用于稀燃汽油机或柴油机尾气NOx捕集的三效催化剂 |
EP4166230A1 (de) * | 2021-10-12 | 2023-04-19 | Johnson Matthey Public Limited Company | Katalysatorartikel für abgassystem eines erdgasmotors |
WO2024115791A1 (en) * | 2022-12-02 | 2024-06-06 | Basf Corporation | Catalyst comprising a sulfur-trap material for the treatment of an exhaust gas stream containing one or more of formaldehyde, nitrogen oxide (no), and hydrocarbons |
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Also Published As
Publication number | Publication date |
---|---|
EP3411143A1 (de) | 2018-12-12 |
KR20180111903A (ko) | 2018-10-11 |
US20200032687A1 (en) | 2020-01-30 |
CN108602051A (zh) | 2018-09-28 |
DE102016101761A1 (de) | 2017-08-03 |
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