WO2002020155A1 - Catalyseur de type absorption/reduction permettant l'elimination de no¿x? - Google Patents
Catalyseur de type absorption/reduction permettant l'elimination de no¿x? Download PDFInfo
- Publication number
- WO2002020155A1 WO2002020155A1 PCT/JP2001/006634 JP0106634W WO0220155A1 WO 2002020155 A1 WO2002020155 A1 WO 2002020155A1 JP 0106634 W JP0106634 W JP 0106634W WO 0220155 A1 WO0220155 A1 WO 0220155A1
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- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- particles
- absorption
- absorbent
- performance
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 43
- 239000002245 particle Substances 0.000 claims abstract description 86
- 239000002250 absorbent Substances 0.000 claims abstract description 41
- 230000002745 absorbent Effects 0.000 claims abstract description 41
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 7
- 150000004706 metal oxides Chemical group 0.000 claims abstract description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 3
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 3
- 238000000746 purification Methods 0.000 claims description 32
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 6
- 150000001340 alkali metals Chemical class 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 5
- 239000004615 ingredient Substances 0.000 abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 45
- 239000000843 powder Substances 0.000 description 37
- 239000000306 component Substances 0.000 description 34
- 239000007789 gas Substances 0.000 description 27
- 239000010948 rhodium Substances 0.000 description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 18
- 229910052697 platinum Inorganic materials 0.000 description 18
- 238000006722 reduction reaction Methods 0.000 description 13
- 229910052703 rhodium Inorganic materials 0.000 description 13
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 13
- 230000002378 acidificating effect Effects 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- 239000000446 fuel Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000003795 desorption Methods 0.000 description 8
- 229910052763 palladium Inorganic materials 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 5
- 239000000969 carrier Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 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
- 238000011068 loading method Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 241000257465 Echinoidea Species 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- KUGRPPRAQNPSQD-UHFFFAOYSA-N OOOOO Chemical compound OOOOO KUGRPPRAQNPSQD-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000555745 Sciuridae Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- 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)
-
- 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
- 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
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1021—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1023—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1025—Rhodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
- B01D2255/2063—Lanthanum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20715—Zirconium
-
- 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
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- 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
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J37/0242—Coating followed by impregnation
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Definitions
- the present invention relates to an exhaust gas purifying catalyst for purifying exhaust gas from an internal combustion engine such as an automobile and, more particularly, to absorbent reduction the NO x purification catalyst for the NO x purification performance was improved.
- the absorption reduction type the NO x purification catalyst combined with lean burn engines constantly fuel is combustion air-fuel ratio under the condition of lean (oxygen-excess), temporarily scan Tiki (stoichiometric air-fuel ratio) - Li Tsu
- the fuel is burned under the condition of (h).
- HC hydrocarbons
- CO hydrocarbons
- NO x is trapped in the absorbent at rie down conditions, it Is released under temporary stoichiometric to rich conditions, and is reduced and purified by the action of a reducing atmosphere and a catalyst.
- the NO x purification catalyst as the catalyst component, platinum, gold, palladium, noble metals such as rhodium is used and as the NO x absorption adsorbents, mosquito re um, alkali such as diisocyanato Li um Metals and basic materials such as alkaline earth metals such as calcium and palladium are used.
- the good UNA Li one bumpers down system that combines air-fuel ratio control and the NO x absorbent is exhausted gas compared in the vicinity conventional three-way catalyst and the stoichiometric air-fuel ratio, improves the CO fuel efficiency, HC, total of the NO x Some success has been achieved in reducing emissions.
- the prior art absorption reduction type the NO x purification catalyst for the exhaust gas temperature is in the low temperature below about 3 0 0 ° C, there is a problem the NO x purification performance can depletion Shii like.
- SO x to a source of sulfur contained a slight amount during combustion to form a the NO x absorbent and the salts, the SO x is not easily desorbed from the NO x absorbent, over time vo chi purification If the performance drops, there is a problem with the ray.
- the invention is a prior art Rukoto to provide a catalyst having different structures, to solve such problems, high the NO x purification performance even at a low temperature, the SO x exhaust gas purification catalyst leaving with improved
- the purpose is to provide. Disclosure of the invention
- the catalyst component is achieved by the absorption reduction type the NO x purification for catalysts, characterized in that the carrier particles and the NO x absorbent particles supported is formed by mixing.
- the exhaust gas purifying catalyst of the present invention is a catalyst in which the carrier particles carrying the catalyst component and the NO x absorbent particles are separate particles, and the carrier particles and the absorbent particles are mixed. It is.
- the NO x is incorporated by absorption into or onto the NO x absorbent particles in a form that is substantially intact in chemical structure.
- the catalyst component such as platinum
- oxidation performance of the oxidation performance as well as HC to the NO ⁇ NO 2 is caused to decrease in the lean conditions. Yotsute thereto, and the absorption performance of the NO x at low temperatures, that the HC purification rate declines Become. Even at high temperatures, the NO x purification rate does not increase.
- the NO x absorbent such as a conventional alkali metal, for absorbing NO x and SO x in the form of nitrates and sulfates, sufficient that these salts are formed up to the inside of the NO x absorbent particles
- the rate of forming salts until the internal and internal to the speed is formed bonds to release the NO x or the like from strong salt is slow, as a result, low absorption and release of such vo chi It is thought to bring efficiency.
- the present invention is Ri Ah separate particles from the vo chi absorber and carrier, loading of constraints to be supported on a carrier like a conventional New Omicron chi absorbent alkali metal etc. Absent. Therefore, the present invention uses vo chi intake adsorbents surface or only near the surface NO chi sufficiently be absorbed as vo chi purification by reduction is possible urchin, a large amount of vo chi absorbent rate by also Ri by the use of absorbent which absorbs vo chi like with a relatively weak bond, eliminates the low absorption and emission efficiency, etc. vo chi, cold New Omicron chi purification performance and so x release It is thought that it can be further improved. BRIEF DESCRIPTION OF THE FIGURES
- FIG. 1 is a model diagram showing one embodiment of the catalyst structure of the present invention.
- FIG. 2 is a model diagram showing a conventional catalyst structure.
- FIG. 3 is a model diagram showing another embodiment of the catalyst structure of the present invention.
- FIG. 4 is a model diagram showing another embodiment of the catalyst structure of the present invention.
- Figure 5 is a graph comparing the NO oxidizing ability of the catalysts.
- FIG. 6 is a graph comparing the SO x desorption properties of the catalysts. BEST MODE FOR CARRYING OUT THE INVENTION
- Noble metals such as platinum, gold, palladium, and rhodium can be used as the catalyst component.
- New Omicron chi Particles that can be absorbed on the surface or inside of the particles in a specific structure can be used.
- or form a salt in a part vo chi is its absorbent particles, its salts may be dissolved in a vo chi absorbent.
- carrier particles among alumina, silica, titania, zirconia, and seria, those having a high specific surface area and a fine form are suitably selected. This is to provide a large contact area with the exhaust gas.
- acid carrier particles are added to the above carrier particles.
- As the acidity carrier particles W0 3 / Z r O 2 , Al Minor silica, zeolite and the like. With this addition,
- NO x purification performance and SO x desorption properties can be further improved. This is because, as described above, catalysts such as platinum originally exhibit a catalytic action on the acidic side, but acidic carrier particles. is acidic condition formed by the addition of, and in the acidic properties carriers, probably because the movement of the NO x and SO x is fast.
- carrier particles are formed by adding WO 3 / ZrO 2 or the like to powder particles having a high specific surface area such as ⁇ -alumina. While ⁇ -alumina has a high specific surface area, it is easy to obtain, while W ⁇ 3 / ZrO 2 by itself has difficulty in obtaining a high specific surface area.
- W0 3 / Z r O 2 as shown in the following Examples are particles were deposited 1VO 3 on the surface of the Z r O 2 particles.
- catalyst components, carrier particles, and catalyst of the present invention comprising the NO x absorbent particles Ri by the general method, the carrier particles and the NO x absorbent particles and the slurries engaged mixed, mono- the slurry It can be obtained by applying to a squirrel base material, drying and firing, and then supporting and drying and firing a catalyst component.
- the carrier particles catalyst component is supported and the NO x absorbent particles are mixed in the slide rie, the slide rie can also be obtained by a applying to drying and baking to physical scan substrate .
- the loading of the catalyst component can be performed by, for example, a precipitation method, a precipitation method, an adsorption method, an ion exchange method, or the like.
- FIGS. 1 to 4 Some embodiments of the absorption reduction-type vo chi purifying catalyst of the present invention is shown in FIGS. 1 to 4 are combined with the catalyst structure of the prior art.
- Figure 1 is a precious metal catalyst component is carried on ⁇ - alumina support particles, vo chi absorbent particles exhibit conditions that exist as separate particles and carrier particles.
- Figure 2 is a prior art absorption reduction type the NO x purification catalyst for, showing a state in which both carried the precious metal and the NO x absorbent catalyst components on the ⁇ - alumina support particles child.
- y of the carrier particles - platinum catalytic component is supported on alumina, rhodium carried on the acidic properties carriers, NO x absorbent particles are their and those of the carrier particles and other particles Indicates a state that exists.
- FIG. 4 shows a state in which an acidic carrier supporting palladium as a catalyst component is further mixed in the embodiment of FIG.
- the size of these components in the absorption reduction type the NO x purification catalyst of the present invention is not particularly necessary to limit, the longest diameter and the average der shortest diameter Ru average particle size (physically fused aggregate If formed, the diameter of the aggregate is 0.5 ⁇ ! -5 / m, more preferably 0.5-2 ⁇ m, and the acidic carrier particles are 0.5 ⁇ -5 ⁇ , more preferably 0.5 ⁇ ! ⁇ 2 ⁇ is a rough guide.
- the catalyst component is 1 to 10 parts by mass, more preferably 2 to 4 parts by mass, and the acid-type carrier particles are 5 to 100 parts by mass of the carrier particles. 0 to 200 parts by mass, more preferably 100 to 200 parts by mass is a rough standard.
- the slurry was coated on a monolith substrate, after drying and calcination, 6 5 0 ° and calcined for C in 1 hour, L a x Z r! _ X O (2 on the physical scan substrate.
- a layer containing x / 2) (x 0. 05) powder particles and ⁇ -alumina powder particles was formed.
- this layer was impregnated with an aqueous solution of dinitrogenamine Pt, dried, and calcined at 500 ° C. for 1 hour to support platinum as a catalyst component.
- the monolith substrate 1 was prepared in the same manner as in Example 1 except that the aqueous solution of dinitrodiammine Pt in Example 1 was reduced to an amount equivalent to 2 g of platinum, and hexammine nitrate Rh was added in an amount equivalent to 1 g of rhodium.
- aqueous solution of dinitrodiammine Pt in Example 1 was reduced to an amount equivalent to 2 g of platinum, and hexammine nitrate Rh was added in an amount equivalent to 1 g of rhodium.
- 2 g of platinum, rhodium lg, La x Z r! _ X ⁇ ( 2 — x / 2 ) (x 0.05) powder particles 100 g, gamma-alumina powder particles 75 A catalyst carrying g was obtained.
- Example 5 Example 5 was repeated except that 1 g of rhodium of hexammine nitrate Rh was replaced by 0.5 g of rhodium of hexaammine nitrate Rh and 0.5 g of palladium of palladium nitrate.
- 2 g of platinum, 0.5 g of rhodium, 0.5 g of palladium, 0.5 g of palladium, and La aZr! submit XO (2 — x / 2 ) ( per liter of the monolith substrate) x 0.05)
- a catalyst carrying 100 g of powder particles and 100 g of WO 3 / ZrO 2 powder particles was obtained.
- Example 1 No Pt 5 6.5 9 6.7 8 6.4
- Example 2 No Rh 5 8, 2 9 8.1 8 6.9
- Example 3 No Pd 8 6.5 9 6.7 86.7
- Example 4 Pt WO 3 / zro 2 5 8.19 9 6.2 77.0
- Example 5 Rh WO 3 / zr O 2 6 0 .1 9 8.2 79.1
- Example 6 P d wo 3 / zro 2 8 5.4.9 9 7.5 8 0.5
- Example 7 R h / P d WO 3 / zro 2 8 8.2 9 8 1 8 1.5 Comparative example 1 P t None 4 1.6 9 1.6 9 8.4
- Example 2 R h None 4 0.1 7 8. 4 6 4.3 Example 3 Pd None 3 5. 6 7 6. 5 6 4.2 Example 4 P t wo 3 / zr ⁇ 2 5 4 1 9 2. 3 6 7.4 Example 5 R h wo 3 / zr O 2 5 3.1 9 3.5 70.1 Example 6 P d wo 3 / zr O 2 7 9, 1 9 4 5 74.5 Example 7 R h / P d wo 3 / zr O 2 9 5.2 9 6.6 7 8.0 Comparative Example 1 No Pt 1 5.2 7 8.1 5 4.1
- Example 2 For the catalysts of Example 2, Example 5, and Comparative Example 1, In a gas atmosphere, the temperature was raised to 250 to 550 ° C for 30 minutes to perform sulfur poisoning.
- the active suppression of the catalyst component is eliminated by disconnecting the vo chi absorption component from the catalyst ingredient carriers, also be ascribed to the relatively weak binding of the SO x and the NO x absorbent.
- the catalyst of the present invention improves the low temperature the NO x purification performance and to improve the SO x desorption properties. Therefore, the temperature range in which high three-way performance can be exhibited is expanded, and a catalyst suitable for purifying diesel exhaust gas can be provided.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Combustion & Propulsion (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Exhaust Gas After Treatment (AREA)
- Treating Waste Gases (AREA)
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20037003403A KR100571688B1 (ko) | 2000-09-08 | 2001-08-01 | 흡수 환원형 NOx 정화용 촉매 |
EP01956778A EP1323470B1 (en) | 2000-09-08 | 2001-08-01 | Absorption/reduction type catalyst for nox removal |
US10/362,994 US6906002B2 (en) | 2000-09-08 | 2001-08-01 | Absorption reduction-type NOx purifying catalyst |
DE60120206T DE60120206T2 (de) | 2000-09-08 | 2001-08-01 | Absorptions-/reduktionskatalysator zur nox-entfernung |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000278679A JP3797081B2 (ja) | 2000-09-08 | 2000-09-08 | 吸収還元型NOx浄化用触媒 |
JP2000-278679 | 2000-09-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002020155A1 true WO2002020155A1 (fr) | 2002-03-14 |
Family
ID=18763806
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2001/006634 WO2002020155A1 (fr) | 2000-09-08 | 2001-08-01 | Catalyseur de type absorption/reduction permettant l'elimination de no¿x? |
Country Status (7)
Country | Link |
---|---|
US (1) | US6906002B2 (ja) |
EP (1) | EP1323470B1 (ja) |
JP (1) | JP3797081B2 (ja) |
KR (1) | KR100571688B1 (ja) |
DE (1) | DE60120206T2 (ja) |
ES (1) | ES2266225T3 (ja) |
WO (1) | WO2002020155A1 (ja) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3528839B2 (ja) * | 2002-05-15 | 2004-05-24 | トヨタ自動車株式会社 | パティキュレート酸化材及び酸化触媒 |
WO2004022225A2 (en) * | 2002-09-09 | 2004-03-18 | Millennium Chemicals Thann Sas | Method for converting nitrogen oxides (nox) in exhaust gases and catalyst useful for it |
JP4236543B2 (ja) | 2003-09-08 | 2009-03-11 | 本田技研工業株式会社 | 窒素酸化物の接触分解のための触媒と方法 |
JP4765382B2 (ja) * | 2005-04-18 | 2011-09-07 | トヨタ自動車株式会社 | 耐熱性を備えた複合酸化物の製法 |
JP4765381B2 (ja) * | 2005-04-18 | 2011-09-07 | トヨタ自動車株式会社 | 耐熱性を備えた複合酸化物の製法 |
RU2370308C1 (ru) | 2005-07-12 | 2009-10-20 | Тойота Дзидося Кабусики Кайся | Катализатор очистки выхлопных газов и способ его приготовления |
EP2145679A1 (en) * | 2008-07-17 | 2010-01-20 | Ford Global Technologies, LLC, A subsidary of Ford Motor Company | Multifunctional Catalyst for Diesel Exhaust Gas Cleaning Applications and Method of its Preparation |
FR2939695B1 (fr) * | 2008-12-17 | 2011-12-30 | Saint Gobain Ct Recherches | Structure de purification incorporant un systeme de catalyse supporte par une zircone a l'etat reduit. |
US10500562B2 (en) * | 2018-04-05 | 2019-12-10 | Magnesium Elektron Ltd. | Zirconia-based compositions for use in passive NOx adsorber devices |
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- 2001-08-01 EP EP01956778A patent/EP1323470B1/en not_active Expired - Lifetime
- 2001-08-01 KR KR20037003403A patent/KR100571688B1/ko not_active IP Right Cessation
- 2001-08-01 ES ES01956778T patent/ES2266225T3/es not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
---|---|
EP1323470B1 (en) | 2006-05-31 |
DE60120206D1 (de) | 2006-07-06 |
EP1323470A1 (en) | 2003-07-02 |
DE60120206T2 (de) | 2007-03-29 |
JP3797081B2 (ja) | 2006-07-12 |
EP1323470A4 (en) | 2004-08-11 |
JP2002079096A (ja) | 2002-03-19 |
KR20030029945A (ko) | 2003-04-16 |
KR100571688B1 (ko) | 2006-04-18 |
US20030181326A1 (en) | 2003-09-25 |
ES2266225T3 (es) | 2007-03-01 |
US6906002B2 (en) | 2005-06-14 |
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