WO2006103781A1 - 排ガスの浄化装置及び排ガスの浄化触媒 - Google Patents
排ガスの浄化装置及び排ガスの浄化触媒 Download PDFInfo
- Publication number
- WO2006103781A1 WO2006103781A1 PCT/JP2005/006242 JP2005006242W WO2006103781A1 WO 2006103781 A1 WO2006103781 A1 WO 2006103781A1 JP 2005006242 W JP2005006242 W JP 2005006242W WO 2006103781 A1 WO2006103781 A1 WO 2006103781A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- exhaust gas
- base material
- gas purification
- internal combustion
- catalyst
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 168
- 238000000746 purification Methods 0.000 claims abstract description 140
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000011248 coating agent Substances 0.000 claims abstract description 36
- 238000000576 coating method Methods 0.000 claims abstract description 36
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 239000007769 metal material Substances 0.000 claims abstract 3
- 239000000463 material Substances 0.000 claims description 101
- 239000002585 base Substances 0.000 claims description 91
- 229910052783 alkali metal Inorganic materials 0.000 claims description 58
- 150000001340 alkali metals Chemical class 0.000 claims description 58
- 238000002485 combustion reaction Methods 0.000 claims description 45
- 229910052751 metal Inorganic materials 0.000 claims description 42
- 239000002184 metal Substances 0.000 claims description 39
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 35
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 35
- 239000000758 substrate Substances 0.000 claims description 23
- 239000000446 fuel Substances 0.000 claims description 20
- 229910000510 noble metal Inorganic materials 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000013508 migration Methods 0.000 claims description 9
- 230000005012 migration Effects 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 229910052703 rhodium Inorganic materials 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 238000005219 brazing Methods 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 238000010306 acid treatment Methods 0.000 claims 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 1
- 229940072033 potash Drugs 0.000 claims 1
- 235000015320 potassium carbonate Nutrition 0.000 claims 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 abstract description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract 4
- 239000011651 chromium Substances 0.000 abstract 4
- 239000004615 ingredient Substances 0.000 abstract 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 2
- 239000007789 gas Substances 0.000 description 81
- 230000000694 effects Effects 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 16
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- 239000010410 layer Substances 0.000 description 13
- 239000011888 foil Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 230000007423 decrease Effects 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 230000006866 deterioration Effects 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052878 cordierite Inorganic materials 0.000 description 3
- 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 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- -1 tita Chemical class 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- 229910002060 Fe-Cr-Al alloy Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 206010027439 Metal poisoning Diseases 0.000 description 1
- GXCLVBGFBYZDAG-UHFFFAOYSA-N N-[2-(1H-indol-3-yl)ethyl]-N-methylprop-2-en-1-amine Chemical compound CN(CCC1=CNC2=C1C=CC=C2)CC=C GXCLVBGFBYZDAG-UHFFFAOYSA-N 0.000 description 1
- 229910002089 NOx Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J33/00—Protection of catalysts, e.g. by coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0225—Coating of metal substrates
-
- 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
- B01J37/0225—Coating of metal substrates
- B01J37/0226—Oxidation of the substrate, e.g. anodisation
-
- 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
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
-
- 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
-
- 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
- F01N3/0828—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
-
- 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
- F01N3/24—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 constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
- F01N3/2807—Metal other than sintered metal
- F01N3/281—Metallic honeycomb monoliths made of stacked or rolled sheets, foils or plates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/902—Multilayered catalyst
- B01D2255/9022—Two layers
-
- 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
- F01N2350/00—Arrangements for fitting catalyst support or particle filter element in the housing
-
- 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
- F01N2450/00—Methods or apparatus for fitting, inserting or repairing different elements
- F01N2450/02—Fitting monolithic blocks into the housing
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Definitions
- the present invention relates to an exhaust gas purification device and an exhaust gas purification catalyst for an internal combustion engine.
- Patent Document 1 Japanese Patent Laid-Open No. 9-85093 (Patent Document 1) describes a NOx occlusion material that has a three-component power of a noble metal, K, Na and Li as a porous carrier. There is a description that NOx purification rate is improved by using.
- Patent Document 2 Japanese Patent Application Laid-Open No. 10-286461
- Patent Document 3 Japanese Patent Application Laid-Open No. 2001-246252
- Patent Document 4 states that the coating of the ⁇ -alumina layer on the metal-cam base material can suppress the separation of the catalyst component.
- an alumina layer is formed by applying an alumina source to a ceramic carrier and firing it before supporting the catalyst material.
- an alumina source to a ceramic carrier and firing it before supporting the catalyst material.
- Patent Document 1 Japanese Patent Laid-Open No. 9-85093
- Patent Document 2 JP-A-10-286461
- Patent Document 3 Japanese Patent Laid-Open No. 2001-246252
- Patent Document 4 Japanese Patent Laid-Open No. 5-184926
- Patent Document 5 International Publication Number WO02 / 020154 A1 Publication
- Patent Document 2 or 3 The content disclosed in Patent Document 2 or 3 was to improve the durability of the catalyst by using a metal knife-cam. However, as a result of our intensive studies, it was found that even if metalno and two cams are used, the purification activity of the catalyst is greatly reduced when the heat endurance treatment of the catalyst is advanced.
- Al and Cr are added to the metal-nozzle cam as constituent elements.
- Cr may react with the catalytically active component and cause a decrease in activity.
- an alkali metal or alkaline earth metal is contained as a catalytically active component, it easily forms a complex oxide with Cr, causing a decrease in activity.
- heat is applied to the metal-cam in the presence of oxygen, the metal-cam constituent element A1 appears on the surface and forms a film of A10.
- Patent Document 4 a technique for performing a-alumina coating on the metal foil-cam surface layer in order to prevent separation of the catalytically active component is disclosed, but an alkali metal is used as the catalytically active component. Or, it is not intended to use alkaline earth metals, and it is not assumed that Cr will react with catalytically active components. Moreover, contact with alkali metal or alkaline earth metal and Cr cannot be suppressed when a catalytically active component is supported only by performing alumina coating.
- Patent Document 5 The technique described in Patent Document 5 is a method in which an alumina source is applied to a ceramic saw-cam to form an alumina layer, and the deterioration of alkali metal or alkaline earth metal by force Cr. None will be disclosed. As described above, Patent Documents 2 to 5 do not suggest or disclose any of the above problems.
- the present invention provides an exhaust gas purification apparatus provided with an exhaust gas purification catalyst in an exhaust gas flow path of an internal combustion engine, wherein the gas purification catalyst includes a base material containing Cr, and a coating covering the base material.
- the catalyst prevents the deterioration of the NOx purification performance of the exhaust gas purification catalyst by suppressing the migration of Cr contained in the base material to the catalytic active component. This is what you can do.
- the catalytically active component may be formed directly on the surface of the film, or may be formed after being supported on a carrier.
- the present invention provides an exhaust gas purification system in which a base material containing Cr and A1 is heat-treated in an oxidizing atmosphere so that a film is formed on the surface of the base material by the base material-precipitated element. ⁇ ⁇ It is in the catalyst manufacturing method.
- the exhaust gas purification apparatus and exhaust gas purification catalyst of the present invention in an internal combustion engine using a catalyst containing at least one of an alkali metal or an alkaline earth metal as a catalytic active component on a metal substrate containing Cr.
- the reaction between Cr and alkali metal or alkaline earth metal can be suppressed, and deterioration of the noble metal by Cr can also be suppressed.
- the NOx purification performance can be prevented from degrading even after heat endurance treatment. This makes it possible to reduce NOx emissions from internal combustion engines.
- FIG. 1 is a graph showing changes in lean NOx purification rate with respect to catalyst inlet gas temperature.
- FIG. 2 A graph showing the change in lean / sticky NOx purification rate with respect to reaction time.
- FIG. 3 is a diagram showing the metal structure of the catalyst, particularly the Cr distribution.
- FIG. 4 is a conceptual diagram schematically showing the structure of a catalyst.
- FIG. 5 is a graph showing the relationship between the thickness of a-alumina film and the lean NOx purification rate.
- FIG. 6 is a graph showing the relationship between the total amount of alkali metal supported and the lean NOx purification rate.
- FIG. 7 is a graph showing the relationship between the total amount of alkali metal supported and the lean NOx purification rate.
- FIG. 8 is a graph showing the relationship between the amount of alumina coating and the lean NOx purification rate.
- FIG. 9 is a diagram showing the relationship between the number of cells and the lean NOx purification rate.
- FIG. 10 is a diagram showing a difference in lean NOx purification rate due to a difference in cell shape.
- FIG. 11 is a schematic configuration diagram showing an exhaust gas purifier according to an embodiment of the present invention.
- FIG. 12 is an explanatory view showing an example of a method for forming a metalno, two-cam base material.
- FIG. 13 is a horizontal sectional view of a metal honeycomb substrate.
- 10 base material, 12 ... exhaust gas purification catalyst, 20 ... alumina support particles, 30 ... catalytically active component, 40 ... ⁇ -alumina coating, 50 ... ⁇ -alumina coating layer, 99 ⁇ Engine, 110 ⁇ Har cam-like structure, 11 la... flat plate, 11 lb... corrugated plate, 120 ⁇ Metal heavy cam base material.
- the present invention provides an exhaust gas purification apparatus provided with an exhaust gas purification catalyst in an exhaust gas flow path of an internal combustion engine, wherein the gas purification catalyst includes a base material containing Cr, and a coating covering the base material. It is composed of a catalytically active component or a catalytically active component and a carrier. By suppressing the migration of Cr in the substrate to the catalytically active component by the film, the NOx purification performance of the exhaust gas purification catalyst is reduced. It is characterized by preventing. As a film covering the base material, hyalumina is considered.
- the present invention provides that the amount of Cr transferred into the catalytically active component after heat treatment of the exhaust gas purifying catalyst in the air at 850 ° CX 300h is 0.5 wt% with respect to the catalytically active component.
- An exhaust purification apparatus for an internal combustion engine is characterized by the following.
- the present invention is a substrate for an exhaust gas purification catalyst containing Cr, comprising a film on the surface of the substrate, and Cr contained in the substrate by the film.
- An exhaust gas purifying catalyst base material characterized by suppressing movement toward a catalytically active component side.
- alkali metal or alkaline earth metal when used as a catalytically active component, if Cr and 0 coexist, alkali metal and alkaline earth metal react with Cr to form a composite oxide.
- the amount of Cr transferred into the catalytically active component after heat treatment of a new exhaust gas purification catalyst in air at 850 ° CX 300h is the catalyst activity.
- a film that can be suppressed to 0.5 wt% below the component is preferable. If it exceeds 0.5wt%, the alkali metal and alkaline earth metal poisoning due to Cr occurs remarkably, causing a decrease in activity.
- the amount of Cr transferred to the catalytically active component after heat treatment in air at 850 ° CX 300h for a new exhaust gas purification catalyst was 0.5 wt% relative to the catalytically active component. It is preferable to form a film that can be suppressed to not more than%.
- the film to be formed on the substrate may be anything as long as the above conditions are satisfied. Meet the above conditions Thus, a decrease in activity due to heat treatment of the catalyst is suppressed.
- the base material targeted by the exhaust gas purifying catalyst of the present invention is one containing Cr, and any base material containing Cr is effective.
- a metal nanocam structure composed of iron-based metal foils with various material strengths such as Cr-A ⁇ Fe can be considered.
- the base material for the exhaust gas purification catalyst of the present invention contains Cr, and the catalytically active component to be supported on this base material contains at least one of an alkali metal and an alkaline earth metal. Is included.
- Cr moves to the alkali metal or alkaline earth metal. Therefore, in order to suppress this movement of Cr, the base material containing Cr A film is provided on the surface. Therefore, the base material in the exhaust gas purifying catalyst of the present invention is a base material having a film provided on the surface of the base material containing Cr so as to be able to carry a catalytically active component.
- the constituent elements of the film are composed of the same elements as all or part of the constituent elements of the substrate. By doing so, the adhesion between the film and the substrate is increased, and a film without damage can be formed, so that the movement of Cr can be suppressed. If the film is composed of elements deposited from the base material, it exhibits a very high degree of suppression effect on the movement of Cr.
- an alumina film may be considered as the film. Further, it is preferable that the amount of Cr, the amount of alkali metal, and the amount of alkaline earth metal contained in the film are each 1 wt% or less of the entire film.
- the base material contains 14 to 26 wt% Cr, 3.0 to 6.5 wt% Al, 0.02 to 0.12 wt% rare earth element containing Y, and the balance is substantially Fe in terms of metal elements
- the foil material can be formed into a no-cam shape and bonded by diffusion bonding, brazing or both.
- a coating with ⁇ -alumina is also suitable.
- a typical metal substrate for example, a typical metal substrate
- the ⁇ -alumina film which is formed by oxidizing the foil itself that constitutes the hard cam in a high-temperature oxidizing atmosphere, is very dense, and the movement of Cr is less likely to cause damage to the film. It exhibits very good properties for inhibition and gives excellent catalyst durability. Therefore, after forming the ⁇ -alumina film by the above method, If the active component is supported, poisoning of the catalytically active component by Cr can be highly suppressed.
- ⁇ -alumina powder and ⁇ -alumina slurry prepared with alumina precursor and made acidic with nitric acid are coated and then dried and fired to form ⁇ -alumina layer Force that can be controlled Cr movement suppression effect is not obtained.
- ⁇ -alumina film treatment when the ⁇ -alumina film treatment is performed, most of the ⁇ -alumina film is composed of chemical bonds of A1 and 0, and the porosity is very fine as 0.1% or less. This can be seen from the fact that the water absorption of the ⁇ -alumina film is almost zero.
- an ⁇ -alumina slurry when coated to form an a-alumina layer, it is composed of a set of a-alumina particles, which is less dense than the former, and therefore more than a few wt%. It has a water absorption rate of
- A1 is an indispensable element for forming an alumina film with a selective acid, and this film prevents the diffusion of Cr into the catalyst layer. Since A1 in the material is consumed, a sufficient amount of A1 additive is required in the base material, and this meaning is also set to a lower limit of 3.0%. However, from the viewpoint of obtaining sufficient acid resistance, the content of A1 is preferably 4.5 wt% or more.
- the A1 high content additive causes hardening and brittleness of the material, so its upper limit is 6.5 wt%.
- Cr is an element that degrades the effectiveness of alkali metals, but it has the effect of improving the adhesion and protection of the alumina film produced by selective oxidation, and is effective in improving acid resistance. Therefore, at least 14 wt% should be added. On the other hand, if it exceeds 26 wt%, the material becomes hard and brittle, and the manufacturability is significantly deteriorated. Therefore, the Cr content is set to 14 to 26 wt%.
- Rare earth elements including Y also have the effect of ensuring the adhesion and protective properties of the alumina film, similar to Cr.For this reason, an additive of 0.02 wt% or more is effective. It is desirable to set the upper limit to 0.12 wt%, since this will impair the effect.
- a metal knife-cam made of Fe-Cr-Al alloy foil is heated to a temperature of 1100 ° C or higher in the atmosphere. It is preferable to warm. Unless the temperature is raised to a temperature of 1100 ° C or higher, alumina with poor compactness other than the ⁇ phase will be formed. Therefore, the effect of preventing Cr diffusion may not be obtained.
- the film thickness is preferably 0.02 ⁇ m or more and 5 ⁇ m or less! /. If the thickness is less than 0.02 ⁇ m, a part of the film, which is difficult to form a film with a certain thickness, may be damaged, and there is a possibility that a reaction between the failure site strength Cr and the catalytically active component may occur. If it is thicker than 5 m, for example, when an ⁇ -alumina film is formed on the surface layer by applying a heat treatment of 1100 ° C or higher to a typical metal substrate, 20Cr-5A ⁇ Fe alloy, Since is an A1 element contained in the metal base material, the amount of in the base material is reduced, which may cause problems with durability as the base material.
- a catalyst having a ⁇ purification rate of 80% or more after 1 minute of lean at 400 ° C is defined as an effective catalyst.
- the ex film thickness is 0.02 ⁇ m or more.
- the present invention can be applied to all exhaust gas purifying apparatuses using an exhaust gas purifying catalyst which is a base material containing Cr and an alkali metal or alkaline earth metal as a catalytic active component.
- Air-fuel ratio of exhaust gas of internal combustion engine Fluctuates from lean to stoichiometric or rich.When the air-fuel ratio is lean, part or all of NOx in the exhaust gas is captured by the exhaust gas purification catalyst, and the air-fuel ratio is stoichiometric or rich.
- alkali metals and alkaline earth metals are generally used as active components, and the catalyst may be exposed to a large amount of oxygen. Many.
- the present invention is very effective as an exhaust gas purification device for such an internal combustion engine.
- the present invention is also effective when a noble metal is contained as a catalytically active component. It is particularly effective against Rh, Pt and Pd among noble metals.
- a noble metal is contained as a catalytically active component. It is particularly effective against Rh, Pt and Pd among noble metals.
- heat treatment is performed by bringing a catalytic active component containing a noble metal into contact with a base material containing Cr, the activity of the noble metal may be significantly reduced. The reason is not clear, but it appears that Cr that appears in the catalyst layer by combining with an alkali metal or alkaline earth metal has some adverse effects on the noble metal. Therefore, if the movement of Cr to the catalyst layer can be suppressed by forming a film on the metal substrate, it is considered that the deterioration of the noble metal due to Cr can also be suppressed.
- NOx purification catalyst When an NOx purification catalyst is installed in the exhaust gas flow path of an internal combustion engine into which the exhaust gas of the air-fuel ratio canon and the exhaust gas with rich or stoichiometric air-fuel flow, NOx is captured as the catalytic active component.
- Any material that can be trapped and purified can be used, but it contains at least one selected alkali metal and alkaline earth metal power as the NOx trapping material, and the lean NOx oxide material and It is desirable to contain at least one of Pt, Pd, Rh and Mn as trapped NOx reducing material when it is rich or rich. This makes it possible to maintain high NOx purification performance during lean and stoichiometric or rich conditions, and after heat treatment.
- the alkali metal contained in the catalyst may be one kind, but more preferably two or more kinds. This is because the temperature that can be captured in the lean region differs depending on the element used. Further, one kind of noble metal may be used, but two or three kinds are preferred. This is because Pt is mainly effective in the oxidation reaction of NO during lean, and Pd and Rh are mainly effective in the reduction reaction of trapped NOx during stoichiometric or rich conditions. Inclusion of Mn increases NOx adsorption performance after heat treatment. It is thought that sintering by alkali metal heat is suppressed by the Mn additive.
- Physical preparation methods such as impregnation method, kneading method, coprecipitation method, sol-gel method, ion exchange method, and vapor deposition method, and preparation methods using chemical reactions, etc. are suitable for the preparation method of the exhaust gas purification catalyst.
- various compounds such as nitric acid compounds, acetic acid compounds, complex compounds, hydroxides, carbonate compounds, organic compounds, metals and metal oxides can be used.
- the active component of the exhaust gas purification catalyst may or may not be supported on a porous carrier.
- the active ingredient is highly dispersed by being supported on the porous carrier.
- the exhaust gas purification performance of the catalyst is improved.
- the porous carrier can be supported on the substrate, the NOx purification performance will be excellent if the loading amount of the porous carrier is 50 g or more and 400 g or less per 1 L of the substrate. If the loading amount of the porous carrier is less than 50 g, the effect of the porous carrier becomes insufficient. If the loading amount is more than 400 g, the specific surface area of the porous carrier itself is reduced, and furthermore, the case where the base material has a hard cam shape is observed.
- porous carrier in addition to alumina, metal oxides such as tita, silica, silica-alumina, zircoure, magnesia, and complex oxides can be used.
- Alumina is particularly preferable. Alumina is considered to have a high heat resistance and a function to enhance the dispersibility of active components such as NOx traps and precious metals.
- an alkali metal such as Li, K, Na, or Cs or an alkali metal such as Mg, Ca, Sr, or Ba is used.
- Potassium earth metal is considered to exist in the form of compounds including acid oxides and the like.
- the total supported amount of alkali metal or alkaline earth metal is preferably from 0.25 mol part to 2.0 mol part in terms of metal elements with respect to 1.9 mol part of the porous carrier.
- the mol part represents the content ratio of each component in terms of mol number.
- the loading amount of B component is 2 mol part with respect to 1.9 mol part of A component. It means that A is 1.9 and B is supported at a ratio of 2 in terms of mol.
- the activity improvement effect by alkali metal or alkaline earth metal support may not necessarily be sufficient, while if it is more than 2.0 mol part This is not preferable because the specific surface area of the alkali metal or alkaline earth metal itself decreases.
- the alkali metal may be K alone, but the activity is further improved when Na or Li is further supported. This is probably because the temperature at which NOx can be captured in the lean region differs depending on the element used. Further, according to the present invention, the reaction between Cr and alkali metal or alkaline earth metal is suppressed, and poisoning by Cr is suppressed even after endurance treatment, so the amount of alkali metal or alkaline earth metal supported on the catalyst is reduced. be able to.
- the total supported amount of Rh, Pt, and Pd is preferably 0.004 mol part to 0.07 mol part in terms of metal element with respect to 1.9 mol part of the porous carrier.
- the total supported amount of Rh, Pt and Pd is less than 0.004 mol part, the activity improvement effect by the noble metal cannot always be sufficient, while when it exceeds 0.07 mol part, the specific surface area of the noble metal itself decreases. Further, it is not preferable because the cost of the catalyst increases.
- the exhaust gas purifying catalyst according to the present invention can be applied in various shapes depending on applications.
- the hard cam shape obtained by coating an iron-based metal foil honeycomb structure made of various alloys including Cr and A1 with a catalytically active component alone or on a porous carrier Can be applied as pellets, plates, granules, powders, and the like.
- the shape of the cell may be any shape such as a triangle, a quadrangle, a hexagon, or a circle. In the case of a hexagon, an extremely high exhaust gas purification capacity can be obtained. This is thought to be because the catalytically active components located at the corners of the cell work efficiently when the cell shape is hexagonal.
- FIG. 11 is an overall configuration diagram showing an embodiment of an internal combustion engine equipped with the exhaust gas purifying apparatus of the present invention.
- the purification apparatus of the present invention includes an exhaust gas purification catalyst 12 in the exhaust gas flow path of the recombinable engine 99, and controls the air-fuel ratio introduced into the catalyst as a control unit (Engine Control Unit, hereinafter referred to as ECU) 11 It is made to control by.
- An air flow sensor 2 and a slot valve 3 are provided in the intake system of the internal combustion engine of the present embodiment, and an oxygen concentration sensor (or A / F sensor) 7 and an exhaust gas purification catalyst inlet gas temperature sensor are provided in the exhaust system. 8 and an exhaust gas purification catalyst 12 are provided.
- the ECU is composed of 1/0 as an input / output interface, LSI, arithmetic processing unit MPU, storage device RAM and ROM that stores many control programs, timer-counter, and so on.
- the above exhaust purification apparatus functions as follows. Intake air to the engine is filtered by the air tailor 1, then measured by the air flow sensor 2, passed through the slot valve 3, further receives fuel injection from the injector 5, and is supplied to the engine 99 as an air-fuel mixture.
- the airflow sensor signal and other sensor signals are input to the ECU 11.
- the ECU 11 evaluates the operating state of the internal combustion engine and the state of the exhaust gas purification catalyst to determine the operating air / fuel ratio, and controls the injection time of the injector 5 to set the fuel concentration of the mixture to a predetermined value.
- the air-fuel mixture sucked into the cylinder is ignited and burned by an ignition plug 6 controlled by a signal from the ECU 11.
- the combustion exhaust gas is led to the exhaust gas purification system.
- the exhaust purification system is equipped with an exhaust gas purification catalyst 12 that is compatible with lean burn, and the stoichiometric operation has its three-way catalytic function to clean NOx, HC, and CO in the exhaust gas, and the lean operation.
- NOx is purified by the NOx trapping function, and at the same time, HC and CO are purified by the combined combustion function. Furthermore, the ECU 11 always determines the NOx purification capacity of the exhaust gas purification catalyst during lean operation based on the judgment and control signals of the ECU 11, and switches to the stoichiometric or rich operation when the NOx purification capacity decreases. By doing so, NOx purification performance can be recovered. According to the exhaust gas purification apparatus described above, NOx emissions can be effectively reduced for all internal combustion engines that perform lean, stoichiometric, or rich operation.
- BNi-5 brazing material is placed between corrugated and flat foils of stainless copper foil containing 20wt% Cr, 5wt% Al and 0.08wt% REM (generic name for a mixture of light rare earth elements such as Ce and La) Then, vacuum brazing treatment was performed at 1200 ° C. for 10 minutes to prepare a metal nonicam base material.
- This metal nanocam base material 400 cells / inch 2 ) was fired at 1100 ° C in the atmosphere while being heated for 1 h to form a thin alumina film on the surface of the metal hard base material. The film thickness was 0.7 m.
- the metal powder-cam substrate was coated with alumina powder and a slurry prepared to be acidic with nitric acid, and then dried and fired to obtain 1.9 mol per 1 liter of the apparent capacity of the hard cam.
- An alumina coated house cam coated with alumina was obtained.
- FIG. 12 shows an example of a method for forming a metal hard cam base material.
- a laminate of stainless steel copper plate 11 la and corrugated plate 11 lb is rolled into a cylindrical shape to form a honeycomb structure.
- the obtained nose-cam-like structure 110 is inserted into the outer cylinder 112 using the press-fitting guide 113 to form a metal heart cam base material.
- This metal-cam base material is heated and held in the atmosphere at a temperature of about 1100 ° C. and fired to form an ex-alumina film on the surface of the metal-cam base material.
- FIG. 13 shows a horizontal sectional view of the obtained metal honeycomb substrate 120.
- the alumina-coated hard cam After impregnating the alumina-coated hard cam with Ce nitrate solution as the first impregnation component, it was dried at 120 ° C and then calcined at 600 ° C for 1 hour.
- the above-mentioned Ce-supported hard cam is impregnated with a mixed solution of K acetate solution, Na nitrate solution, Li nitrate solution and Ti sol, and then dried at 200 ° C, followed by 600 Baked at ° C for 1 hour.
- the above-mentioned Ce, K, Na, Li, Ti-supported hermum was mixed with dinitrodiammine Pt nitric acid solution, di-throdiamine Pd nitric acid solution, nitric acid Rh solution, nitric acid Mn and acetic acid K.
- the mixed solution was impregnated, dried at 200 ° C, and then calcined at 600 ° C for 1 hour.
- the K raw materials contained in the second and third impregnation liquids were the same.
- an endurance treatment an electric furnace in the atmosphere of 850 ° CX 300h Heat treatment was performed.
- Comparative Example Catalyst 1 was obtained by the same preparation method as in Example Catalyst 1 except that the a-alumina film formation treatment was not performed.
- a NOx purification performance test was conducted under the following conditions.
- a lOcc double cam catalyst was fixed in a quartz glass reaction tube. This reaction tube was introduced into an electric furnace, and the heating was controlled so that the temperature of the gas introduced into the reaction tube was 200 ° C to 500 ° C.
- the gas introduced into the reaction tube is a model gas that is assumed to be exhaust gas when an automobile engine is operated at a stoichiometric air-fuel ratio (hereinafter referred to as a stoichiometric model gas), and the automobile engine is operated in a lean manner.
- a model gas (hereinafter referred to as a “line model gas”) that assumes the exhaust gas used when performing the operation was switched every 3 minutes and introduced.
- the composition of the stoichiometric model gas is NOx:
- the composition of lean model gas is NOx: 600ppm, C H: 500ppm, CO: 0.1%,
- the lean NOx purification rate was determined by the following equation.
- Lean NOx purification rate (%) ((NOx concentration in the first stage of the catalyst after switching to lean) 1 (NOx concentration in the second stage of the catalyst after switching to lean)) ⁇ (Switching to lean 1 NOx concentration before catalyst in minutes) X 100
- Evaluation Method 1 The method for evaluating the performance of the catalyst by the above method is referred to as Evaluation Method 1.
- Example Catalyst 1 and Comparative Example Catalyst 1 were evaluated by Evaluation Method 1. The results are shown in Figs.
- the catalyst 1 of the example in which the ⁇ -alumina film treatment was previously applied to the metal-cam base material showed higher lean NOx purification performance than the catalyst 1 of the comparative example.
- the activity in the lean region is mainly due to the action of base points in the catalyst, ie alkali metals. Therefore, it is clear that the formation of the a-alumina film suppresses the deterioration of the alkali metal.
- Fig. 2 shows the NOx purification rate in the stoichiometric and lean regions at 350 ° C for both catalysts. The NOx purification rate of the catalyst at this time was estimated by the following equation.
- NOx purification rate (%) ((NOx concentration before catalyst)-(NOx concentration after catalyst)) / (catalyst upstream)
- Example Catalyst 1 shows high performance not only in the lean region but also in the stoichiometric region.
- the activity in the stoichiometric region is mainly due to the action of noble metals in the catalyst. Therefore, it is clear that the deterioration of the noble metal is suppressed by forming the ⁇ -alumina film.
- Example catalyst 1 and Comparative example catalyst 1 the Cr content in each catalyst component was measured, and in terms of metal element, Example catalyst 1 was 0.07 wt%, whereas Comparative example was For catalyst 1, it was 2 wt%.
- Example Catalyst 1 and Comparative Example Catalyst 1 the structure of the catalyst was examined by EPMA (Electron Probe Micro Analyzer) to determine the distribution state of Cr. The results are shown in Figure 3. As shown in Fig. 3 (a), the catalyst of Example 1 treated with ⁇ -alumina coating hardly transfers Cr to the catalyst layer, whereas a-in Fig. 3 (a). It can be seen that Cr was transferred to the catalyst layer in Comparative Example Catalyst 1 which was not treated with the alumina coating. From this result, it is clear that the migration of Cr to the catalyst layer is suppressed by the ⁇ -alumina coating treatment.
- EPMA Electro Probe Micro Analyzer
- Comparative Example Catalyst 2 was prepared by the same preparation method as in Example Catalyst 1.
- 10 is a base material
- 20 is an alumina carrier particle
- 30 is a catalytically active component
- 40 is an ⁇ -alumina coating
- 50 is an ⁇ -alumina coating layer.
- Comparative Example Catalyst 3 was prepared by the same preparation method as Example Catalyst 1 except that the temperature and holding time when the substrate was acid-treated in the atmosphere were 800 ° C and 1 hour, respectively. .
- the Example Catalyst 1 oxidized at 1100 ° C had an activity of more than 90% at 400 ° C, indicating high NOx purification activity.
- Comparative Catalyst 3 with an oxidation treatment temperature of 800 ° C did not reach 70% of the activity at 400 ° C, and the NOx purification activity was insufficient.
- FIG. 5 shows the results of lean NOx purification at 400 ° C.
- the thickness of the ⁇ -alumina film is 0.02 m or more and 5 m or less
- the activity at 400 ° C exceeds 80%.
- the Cr content in the catalytically active component was 0.50 wt% in terms of metal element. Therefore, it is clear that when the ⁇ -alumina film thickness is 0.02 m or more and 5 m or less, high NOx purification activity is exhibited.
- a catalyst prepared by the same method as in Example Catalyst 1 was evaluated by Evaluation Method 1 except that the total supported amount of alkali metal was changed.
- the composition ratio of the alkali metal was the same as in Example Catalyst 1. The result is shown in FIG. As shown in Fig. 6, when the total supported amount of alkali metal (Li + Na + K) is 0.25 mol / L or more and 2.0 mol / L or less, the activity at 400 ° C exceeds 80% and high purification is achieved. Indicates the rate.
- Example catalyst 1 Prepared by the same method as in Example catalyst 1 except that the amount of noble metal supported was changed
- the evaluated catalyst was evaluated by Evaluation Method 1.
- the composition ratio of the noble metal was the same as in Example Catalyst 1.
- the results are shown in FIG. As shown in Fig. 7, when the total amount of precious metal supported (Rh + Pt + Pd) is 0.004 mol / L or more and 0.07 mol / L or less, the activity at 300 ° C exceeds 30%, high! Indicates the rate.
- a catalyst prepared by the same method as in Example Catalyst 1 was evaluated by Evaluation Method 1 except that the alumina coating amount was changed.
- the results are shown in FIG. As can be seen from Fig. 8, when the amount of alumina coat is 50g / L or more and 400g / L or less, the activity at 300 ° C exceeds 30%, indicating a high purification rate.
- a catalyst having a different number of cells was prepared by the same preparation method as in Example Catalyst 1 except that the number of cells of the metal hard base material was changed to 600 cells and 900 cells.
- Figure 9 shows the results of the lean NOx purification rate at 300 ° C. As can be seen from Fig. 9, when the number of cells exceeds 600, the activity at 300 ° C exceeds 40%, indicating a high NOx purification rate. Therefore, it is clear that the catalyst shows high NOx purification activity when the number of cells exceeds 600 cells.
- a catalyst having a changed cell shape was prepared by the same preparation method as in Example Catalyst 1 except that the cell shape of the metal shell-cam substrate was changed to a hexagonal cell.
- Figure 10 shows the results of the lean NOx purification rate at 300 ° C. As shown in Fig. 10, when the cell shape is hexagonal, the activity at 300 ° C exceeds 40%, indicating a high NOx purification rate. It is clear that when the cell shape is hexagonal, the catalyst shows high NOx purification activity.
- the exhaust gas purification apparatus and exhaust gas purification catalyst of the present invention can be applied to purify exhaust gas from an internal combustion engine such as an automobile.
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Abstract
Description
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EP05727942A EP1867389A1 (en) | 2005-03-31 | 2005-03-31 | Apparatus for purifying exhaust gas and catalyst for purifying exhaust gas |
JP2007510303A JPWO2006103781A1 (ja) | 2005-03-31 | 2005-03-31 | 排ガスの浄化装置及び排ガスの浄化触媒 |
US11/909,760 US20090148357A1 (en) | 2005-03-31 | 2005-03-31 | Apparatus and catalyst for purifying exhaust gas |
PCT/JP2005/006242 WO2006103781A1 (ja) | 2005-03-31 | 2005-03-31 | 排ガスの浄化装置及び排ガスの浄化触媒 |
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EP2772302A1 (en) | 2013-02-27 | 2014-09-03 | Umicore AG & Co. KG | Hexagonal oxidation catalyst |
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CN110997142B (zh) * | 2017-08-08 | 2022-10-11 | 株式会社科特拉 | 排气净化用的金属基材和使用该金属基材的排气净化装置 |
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JPH07316746A (ja) * | 1994-05-27 | 1995-12-05 | Nippon Steel Corp | 触媒メタル担体 |
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JP2003144926A (ja) * | 2001-11-19 | 2003-05-20 | Hitachi Ltd | 内燃機関の排ガス浄化触媒、浄化方法及び浄化装置 |
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DE69624890T2 (de) * | 1995-09-25 | 2003-03-27 | Nippon Oil Co., Ltd. | Filter zur Abscheidung von Russpartikeln aus Abgas und Vorrichtung zur Verwendung desselben |
DE69727819T2 (de) * | 1997-08-20 | 2004-11-04 | Calsonic Kansei Corp. | Metallfolie für einen metallischen Katalysatorträger und damit arbeitender metallischer Katalysator |
KR100310555B1 (ko) * | 1998-07-07 | 2002-01-12 | 김문찬 | 디젤엔진배출가스후처리장치 |
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JP4119218B2 (ja) * | 2002-10-16 | 2008-07-16 | 忠弘 大見 | 水分発生用反応炉の白金コーティング触媒層の形成方法 |
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2005
- 2005-03-31 JP JP2007510303A patent/JPWO2006103781A1/ja active Pending
- 2005-03-31 WO PCT/JP2005/006242 patent/WO2006103781A1/ja active Application Filing
- 2005-03-31 US US11/909,760 patent/US20090148357A1/en not_active Abandoned
- 2005-03-31 EP EP05727942A patent/EP1867389A1/en not_active Withdrawn
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JPS5787837A (en) * | 1980-11-20 | 1982-06-01 | Toyota Motor Corp | Production of catalyst for purification of waste gas |
JPH07316746A (ja) * | 1994-05-27 | 1995-12-05 | Nippon Steel Corp | 触媒メタル担体 |
JPH08299808A (ja) * | 1995-05-12 | 1996-11-19 | Nippon Steel Corp | 耐酸化性、耐久性に優れた触媒用メタル担体の製造方法 |
JPH08332394A (ja) * | 1995-06-07 | 1996-12-17 | Calsonic Corp | 排気浄化用金属担体触媒およびその製造方法 |
JP2003144926A (ja) * | 2001-11-19 | 2003-05-20 | Hitachi Ltd | 内燃機関の排ガス浄化触媒、浄化方法及び浄化装置 |
Cited By (5)
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JP2007014831A (ja) * | 2005-07-05 | 2007-01-25 | Nippon Steel Materials Co Ltd | 優れた高温耐酸化性を有する排気ガス浄化用触媒コンバータ |
JP2007152269A (ja) * | 2005-12-07 | 2007-06-21 | Hitachi Ltd | 内燃機関の排ガス浄化装置及び排ガス浄化触媒 |
US7772149B2 (en) | 2005-12-07 | 2010-08-10 | Hitachi, Ltd. | Exhaust gas purification apparatus for an internal combustion engine and a catalyst for purifying exhaust gas |
CN110280314A (zh) * | 2019-07-16 | 2019-09-27 | 中国科学院兰州化学物理研究所 | 一种提高锰基低温scr催化剂抗水和防尘性能的方法 |
CN110280314B (zh) * | 2019-07-16 | 2021-07-23 | 中国科学院兰州化学物理研究所 | 一种提高锰基低温scr催化剂抗水和防尘性能的方法 |
Also Published As
Publication number | Publication date |
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EP1867389A1 (en) | 2007-12-19 |
US20090148357A1 (en) | 2009-06-11 |
JPWO2006103781A1 (ja) | 2008-09-04 |
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