CN105792929B - Exhaust gas purifying catalyst and its manufacturing method - Google Patents
Exhaust gas purifying catalyst and its manufacturing method Download PDFInfo
- Publication number
- CN105792929B CN105792929B CN201480066003.3A CN201480066003A CN105792929B CN 105792929 B CN105792929 B CN 105792929B CN 201480066003 A CN201480066003 A CN 201480066003A CN 105792929 B CN105792929 B CN 105792929B
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- Prior art keywords
- catalyst
- manufacturing
- catalyst layer
- zirconium
- exhaust gas
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- 239000003054 catalyst Substances 0.000 title claims abstract description 183
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 25
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 24
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 22
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 17
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 15
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 14
- 239000010948 rhodium Substances 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 13
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000969 carrier Substances 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 69
- 239000007789 gas Substances 0.000 claims description 40
- 150000001553 barium compounds Chemical class 0.000 claims description 23
- 239000011268 mixed slurry Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 230000000996 additive effect Effects 0.000 claims description 19
- 239000000654 additive Substances 0.000 claims description 16
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 10
- 150000002940 palladium Chemical class 0.000 claims description 10
- 150000003283 rhodium Chemical class 0.000 claims description 10
- 150000003755 zirconium compounds Chemical class 0.000 claims description 10
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
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- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000004615 ingredient Substances 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 6
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 5
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 3
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 3
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 19
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- 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
- 238000002360 preparation method Methods 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 3
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- 239000002253 acid Substances 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 2
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- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
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- 239000007800 oxidant agent Substances 0.000 description 2
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- 229910052697 platinum Inorganic materials 0.000 description 2
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- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
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- 230000004931 aggregating effect Effects 0.000 description 1
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- 229910052791 calcium Inorganic materials 0.000 description 1
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- 230000003750 conditioning effect Effects 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
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- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—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
- F01N3/101—Three-way catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
- B01J35/45—Nanoparticles
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- B01D2255/20—Metals or compounds thereof
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- B01D2255/2061—Yttrium
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- B01D2255/2063—Lanthanum
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- B01D2255/2092—Aluminium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/40—Mixed oxides
- B01D2255/407—Zr-Ce mixed oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
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- 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
- B01J37/04—Mixing
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2370/00—Selection of materials for exhaust purification
- F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
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- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Mechanical Engineering (AREA)
- Toxicology (AREA)
- General Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (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)
Abstract
The catalyst that dispersion degree the purpose of the present invention is to provide the catalytic metal in the exhaust gas purifying catalyst being made of comprising a variety of catalytic metals and catalyst layer simple layer is high and catalytic performance is high.In addition, manufacturing method of the manufacturing method as the catalyst the purpose of the present invention is to provide the catalyst that can be reliably loaded in the case of without using aqueous slkali.The present invention relates to a kind of exhaust gas purifying catalysts, it is forms the exhaust gas purifying catalyst that single catalyst layer forms on supporter, wherein, catalyst layer is in the Catalytic Layer for having palladium and rhodium with the supported on carriers that cerium oxide zirconia composite oxide mixes by inorganic oxides such as aluminium oxide, and the ratio between the zirconium concentration on the surface of catalyst layer and cerium concentration (SZr/SCe) relative to the zirconium concentration at the interface with supporter and the ratio between cerium concentration (C of catalyst layerZr/CCe) it is 1.05~6.0 times.
Description
Technical field
The present invention relates to exhaust gas purifying catalyst and its manufacturing method, more particularly to one be suitable as in purification exhaust gas
The catalyst of the three-way catalyst of carbonoxide, hydrocarbon and nitrogen oxides.
Background technology
As exhaust gas purifying catalyst, using by the harmful substance contained in exhaust gas i.e. carbon monoxide (CO), nytron
Object (HC) and nitrogen oxides (NOx) oxidation or the three-way catalyst for restoring and being carried out at the same time purification.About the composition of the catalyst,
Outside as the general metal oxide carrier such as the carrier of supported catalyst metal, alumina, also answered using Ceria-zirconia
Close the storage oxygen species such as oxide.In catalyst containing storage oxygen species (OSM), ability is discharged using the absorption of the oxygen based on OSM,
The redox reaction of 3 kinds of harmful substances (CO, HC and NOx) can easily and efficiently be carried out.In addition, in three-way catalyst, as
Catalytic metal, mostly containing noble metals such as platinum of more than two kinds, palladium, rhodiums.For these noble metals, respectively it is easy to having for purification
Evil substance is different, therefore by combining a variety of different noble metals, can remove effectively 3 kinds of harmful substances.
Here, containing, as problem is become in the catalyst of catalytic metal, catalytic metal occurring there are many noble metal
Between alloying when, be unable to give full play out intended catalyzed performance.Therefore, in the case of a variety of catalytic metals of application, lead to
Being commonly formed makes catalyst layer be the structure being made up of multiple layers and the waste gas purification of catalytic metal is respectively configured in each catalyst layer urge
Agent.Palladium is configured in the first coating, is configured with platinum and rhodium in the second coating for example, describing in patent document 1
Exhaust gas purifying catalyst.
But the catalyst for being formed with multiple catalysts layer in this way needs the catalysis to being formed in the making of catalyst
Oxidant layer carries out the manufacturing processes such as the preparation of slurry, the coating on supporter and calcining respectively, and by single catalyst layer structure
Into catalyst compare, manufacturing process's number increases, and becomes catalyst of high cost.
In this context, as using a variety of catalytic metals and making the catalyst that catalyst layer is simple layer, special
Following catalyst has been recorded in sharp document 2：Using rhodium and palladium as catalytic metal, 2 kinds of Ceria-zirconia composite oxygens are used
Compound is as carrier.The catalyst inhibits catalytic metal by loading different catalytic metals respectively on 2 kinds of carriers
Alloying.
As for manufacturing the method for exhaust gas purifying catalyst discussed above, it is however generally that apply following method：
In the slurry comprising carrier add catalytic metal salt after, the pH for making slurry using aqueous slkali rises, so as to make catalytic metal with
The form of insoluble compound is precipitated.Make the pH of the addition due to catalytic metal salt and the slurry in acidity by using aqueous slkali
Rise, thus catalytic metal is made to be fixed on carrier.About this point, described in patent document 2 using tetraethyl hydrogen-oxygen
Change carrying method of the ammonium (TEAH) as the catalytic metal of aqueous slkali.Specifically, in order to which load is different respectively on 2 kinds of carriers
Catalytic metal, first, in the slurry comprising the first carrier add rhodium salt and in highly acid when, add TEAH and make on pH
It rises, so as to which rhodium is precipitated.Then, second of carrier is made to be suspended in the slurry, in addition palladium salt again in acid slurry
It is middle to add TEAH and pH is made to increase again, palladium is precipitated.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 11-151439 bulletins
Patent document 2：Japanese Unexamined Patent Application Publication 2010-521302 bulletins
Invention content
Problem to be solved by the invention
But the catalyst of patent document 2 does not have adequately only in the practical application as exhaust gas purifying catalyst
Change performance, thus expect further improving for catalytic activity.Particularly as the manufacturing method of the catalyst, by using
The catalyst that aqueous slkali forms catalytic metal precipitation is difficult to become the high catalyst of catalytic activity.
Therefore, the purpose of the present invention is to provide given up comprising a variety of catalytic metals and catalyst layer by what simple layer was formed
There is the catalyst of higher purifying property in gas cleaning catalyst.It can be without using alkali soluble the present invention also aims to provide
Catalytic metal is reliably made to precipitate into manufacturing method of the manufacturing method on carrier as the catalyst in the case of liquid.
The method for solving problem
For this purpose, the present inventors is to catalytic performance, good exhaust gas purifying catalyst conducts in-depth research, and have in mind
In catalytic metal to the load condition of carrier.At this point, for the catalyst of above-mentioned patent document 2, it is contemplated to：By urging
Change the interim load of metal, adjusted using the pH of aqueous slkali etc., the catalytic metal being precipitated comes off, is reconfigured.Specifically
For, it is believed that in for making the addition of the catalytic metal salt of second of catalytic metal precipitation, adding the stage of aqueous slkali, first analyse
Go out to the first catalytic metal dissolution on carrier, be reconfigured on another carrier.Then, the catalysis being precipitated using aqueous slkali
Metal is precipitated in the form of hydroxide, is easily be combined with each other and coarsening.The present inventors thinks as a result, by inhibiting
Reliably supported catalyst metal while the reconfiguration of above-mentioned catalytic metal, precipitation in the form of hydroxide, can realize
Catalytic performance further improves, so as to obtain the exhaust gas purifying catalyst of the present invention.As a result, to obtained catalyst into
Go detailed analysis, as a result, it has been found that, when the ratio between the zirconium concentration of catalyst layer surface and cerium concentration (zirconium concentration/cerium concentration) are high,
Load condition of the catalytic metal on carrier becomes reliable, so as to contemplate the exhaust gas purifying catalyst of the present invention.
That is, the present invention relates to a kind of exhaust gas purifying catalyst, formed to form single catalyst layer on supporter
Exhaust gas purifying catalyst, wherein, catalyst layer be by aluminium oxide, cerium oxide, zirconium oxide at least any one form
The supported on carriers that mixes of inorganic oxide and Ceria-zirconia composite oxides have the catalyst layer of palladium and rhodium,
And the zirconium concentration (S on the surface of catalyst layerZr) and cerium concentration (SCe) the ratio between (SZr/SCe) relative to catalyst layer and support
Zirconium concentration (the C at the interface of bodyZr) and cerium concentration (CCe) the ratio between (CZr/CCe) it is 1.05~6.0.
In the exhaust gas purifying catalyst of the present invention, catalyst layer is simple layer, and supported on carriers have palladium and rhodium this 2
Kind is as catalytic metal.Moreover, the catalyst of the present invention is characterized in that following aspect：(zirconium is dense for the ratio between zirconium concentration and cerium concentration
Degree/cerium concentration) near the surface of catalyst layer higher than near interface with supporter.For the catalyst of such present invention
For, the dispersion degree of catalytic metal is high, and catalytic performance (particularly CO oxidabilities, NOx reducing powers) is high.
About zirconium/cerium concentration (SZr/SCe、CZr/CCe), the value (S on the surface of catalyst layerZr/SCe) relative to catalyst layer
The interface with supporter value (CZr/CCe)((SZr/SCe)/(CZr/CCe)) be 1.05~6.0, be preferably 1.1~5.0, especially
Preferably 1.1~3.5.If less than 1.05, the tendency that the durability with catalytic metal becomes inadequate, if more than 6.0,
The tendency that dispersion degree with catalytic metal reduces.
The zirconium on the surface as catalyst layer/cerium concentration ratio (SZr/SCe), from catalyst layer surface up to support
The place that locates of the depth direction of catalyst layer until the interface of body can be applied from the most surface of catalyst layer to branch
The analysis result at the place that locates for the depth that 5~10 μm of support body side.In addition, the interface with supporter as catalyst layer
Zirconium/cerium concentration (CZr/CCe), it can apply from the interface with supporter to the place that locates of the depth of 5~10 μm of surface side
Analysis result.Above zirconium concentration/cerium concentration (SZr/SCe、CZr/CCe) electron ray microanalyzer (EPMA) can be passed through
To measure.
Hereinafter, each structure of the exhaust gas purifying catalyst of the present invention is described in detail.
As carrier, it is used together with inorganic oxides such as aluminium oxide compound as the Ceria-zirconia of storage oxygen species
Oxide (CZ).About CZ, preferably Zirconium oxide is by quality ratio relative to the ratio (zirconium oxide/cerium oxide) of cerium oxide
95/5~5/95.It, can the alkaline earth elements such as the oxide containing rare earth elements such as yttrium, lanthanum, praseodymiums, magnesium, calcium in addition, as additive
One or more of oxide.The content of CZ is preferably 20~80 mass % relative to the quality of catalyst entirety.
As inorganic oxide, can use more than any one in aluminium oxide, cerium oxide, zirconium oxide etc., it is especially excellent
Select aluminium oxide.It, can also be doped with rare earth elements such as yttrium, lanthanum, praseodymiums as aluminium oxide, preferably gama-alumina.Inorganic oxide
Content is preferably 20~80 mass % relative to the quality of catalyst layer entirety.
As catalytic metal, both palladium and rhodium are included.The load capacity of catalytic metal relative to carrier be preferably 0.1~
2.5 mass %.If less than 0.1 mass %, be difficult to obtain sufficient catalytic performance, if more than 2.5 mass %, become without
Ji and the aggregation for easily causing catalytic metal.
In catalyst layer, in addition to above-mentioned carrier and catalytic metal, further preferably contain barium compound.If zirconium/cerium ratio upper
In the range of the stating and also catalyst containing barium, then be easily made into CO oxidizing forces and the higher catalyst of NOx reducing powers.As barium
Object is closed, preferably optionally from barium sulfate, barium carbonate, barium monoxide.These barium salts are in not used exhaust gas purifying catalyst mostly with sulphur
The form of sour barium or barium carbonate exists, and is mostly present in catalyst layer in the form of barium carbonate or barium monoxide using rear in catalyst
In.
Relative to the quality that whole ingredients in catalyst layer are converted into oxide, the content of barium compound is to be converted into
The quality meter of barium monoxide is preferably 0.1~10 mass %, more preferably 1.0~6.0 mass %.It is if difficult less than 0.1 mass %
To obtain the additive effect of barium compound.The upper limit of content is without especially limiting, even if addition more than 10 mass %, barium chemical combination
The additive effect of object is also difficult to further improve.The grain size of barium compound is preferably 0.01 μm less than 2.0 μm.Even if grain
Diameter is less than 0.01 μm, it is also difficult to expect further improving for additive effect, the poly- of barium compound is easily formed in catalyst layer
Glomeration.In the case of aggregation block as formation, the adhesiveness of catalyst layer declines.If the grain size of barium compound is 2.0 μm
More than, then catalytic performance is difficult to improve.Shape of particle preferably spherical or plate.
The exhaust gas purifying catalyst of the present invention is in the branch being made of structures such as ceramic honeycomb, metal beehive, non-woven fabrics
Has the catalyst of catalyst layer discussed above on support body.
As the method for the exhaust gas purifying catalyst for manufacturing the present invention discussed above, following manufacturer can be applied
Method：Be included in addition palladium salt in Ceria-zirconia composite oxides and the carrier paste that forms of inorganic oxide suspension and
Rhodium salt and prepare the process of the mixed slurry of precursor as catalyst layer and mixed slurry be coated on supporter and is formed
The process of the catalyst precarsor layer of individual layer, in the carrier paste in the stage of the addition palladium salt and rhodium salt for the process for preparing mixed slurry
Inside contain zirconium compounds.
In the manufacturing method of the present invention, in addition as in the palladium salt of catalytic metal salt and the stage of rhodium salt, have in suspension
Contain zirconium compounds as additive in the slurry of carrier.It is high for catalytic activity by the catalyst that the preparation method of the present invention obtains
Catalyst particularly can effectively observe that the purifying rate of purification ingredient (CO, HC, NOx) reaches 50% temperature (T50) it is low
Wen Hua.This is considered since palladium and rhodium be not easy to reconfigure on carrier, the reason so as to reliably be loaded.Catalytic gold
Category can so be reached reliable load condition and is considered due to being catalyzed when can inhibit as being loaded using aqueous slkali
Metal is precipitated in the form of hydroxide, and catalytic metal is carried on carrier in the form of an ion.Moreover, it is not easy to as catalytic gold
Belong to the catalysis generated like that when being precipitated in the form of hydroxide caused by the combination between catalytic metal hydroxide
The coarsening of metal.
Hereinafter, the manufacturing method of the present invention is described in detail.It will be as the Ceria-zirconia combined oxidation of carrier
Object and inorganic oxide are suspended in water, prepare carrier paste.The additive amount of each carrier is whole relative to obtained catalyst layer
Body preferably makes inorganic oxide be 20~70 mass %, Ceria-zirconia composite oxides is made to be 20~70 mass %.System
During standby carrier paste, preferably crush, mix and make carrier become uniformly stipulated that size distribution.Size distribution is preferably
0.1~20 μm.It should be noted that Ceria-zirconia composite oxides and inorganic oxide can apply with as exhaust gas
Cleaning catalyst is formed in the same substance of the type being described above, grain size.
When preparing above-mentioned carrier paste, preferably mixed with together with Ceria-zirconia composite oxides and inorganic oxide
Cooperate to carry out for the insoluble barium compound of additive slurried.By also adding insoluble barium chemical combination in addition to zirconium compounds
Object, the readily available higher catalyst of catalytic performance.As long as insoluble barium compound is added before catalytic metal is added, then
It no matter before and after the preparation of carrier paste, can add at any time, but with being used as carrier preferably when preparing carrier paste
Ceria-zirconia composite oxides, inorganic oxide is added together.Since insoluble barium compound is particle shape,
Therefore by crushing, mixing together with the carrier of identical particle shape and slurried, it is equal to thus tend to prepared sizes distribution
Even mixed slurry.
As insoluble barium compound, preferably barium sulfate or barium carbonate, particularly preferred barium sulfate.Relative to will be obtained
Whole ingredients in catalyst layer are converted into the quality of oxide, and the additive amount of insoluble barium compound is to be converted into barium monoxide
Quality meter, preferably 1.0~10 mass %.Here, in the present invention, as barium compound, using insoluble compound.It is solvable
Property barium compound have in the surface micro disperses of Ceria-zirconia composite oxides so as to hinder to absorb the ability for releasing oxygen
Tendency, and be prone to be segregated, it is difficult to it is uniformly dispersed in catalyst layer.On the other hand, it is applying as in the present invention
In the case of insoluble barium compound, shape of particle can be kept in carrier paste, therefore will not be answered in Ceria-zirconia
It closes oxide surface to hinder to absorb the ability for releasing oxygen, barium ingredient can be made to be uniformly dispersed in catalyst layer.It needs to illustrate
, as insoluble barium compound, can apply same in the grain size being described above with the structure as exhaust gas purifying catalyst
The substance of sample.
Then, as the palladium salt of catalytic metal salt and rhodium salt, preparing becomes catalyst layer for addition in above-mentioned carrier paste
Precursor mixed slurry.As catalytic metal salt, the general water-soluble compounds such as nitrate, acetate can be used,
Preferably nitrate.The additive amount of each catalytic metal salt preferably makes the range that palladium is 0.1~2.5 mass % relative to carrier, makes
Rhodium is the range of 0.1~0.5 mass %.
As the opportunity of addition zirconium compounds, preferably when prepared by above-mentioned mixed slurry and addition palladium salt and rhodium salt it
Before.It is more than any one in the preferred zirconyl nitrate of zirconium compounds, zirconium acetate, zirconia sol, particularly preferred zirconyl nitrate.Phase
For whole ingredients in obtained catalyst layer to be converted into the quality of oxide, the additive amount of zirconium compounds is preferably to change
The quality meter for being counted as zirconium oxide reaches the mode of 0.5~5.0 mass % and is added.If the additive amount, then can obtain
The Zr/Ce stated than catalyst, the dispersion degree that is easily made into catalytic metal in obtained catalyst is high, catalytic performance is also high
Catalyst.
It, can be unlike the manufacturing method described in patent document 2 by adding zirconates in the manufacturing method of the present invention
Catalytic metal is made to be fixed on carrier in the case of using aqueous slkali, therefore catalytic metal can be inhibited in the form of hydroxide
Precipitation.The pH for adding the mixed slurry after catalytic metal salt is changed value according to the additive amount of catalytic metal salt, but
Particularly it is mostly about 3.0~about 5.0 under the implementation condition of the present invention mostly in the range of about 2.5~about 6.0.According to this hair
It is bright, catalytic metal can be made reliably to precipitate on carrier in the case where not adding aqueous slkali after catalytic metal salt is added.
Precipitation in catalytic metal is insecure, in the work that the mixed slurry added with catalytic metal is made to be dried, calcine
In sequence, catalytic metal is fallen off sometimes, even if but the catalytic metal that is precipitated by the manufacturing method of the present invention done
Coming off for catalytic metal will not occur durings dry, calcining etc..
For mixed slurry made above, preferably with respect to mixed slurry so that whole catalyst in slurry into
It is prepared by the mode that the solid content divided reaches 20~50 mass %.Obtained mixed slurry is on supporter is applied to
And after forming the catalyst precarsor layer of individual layer, it is calcined and forms catalyst layer, so as to manufacture exhaust gas purifying catalyst.
The calcination temperature of supporter is preferably 400~700 DEG C.When mixed slurry is applied on supporter, acetic acid, water can be used
Conditioning agents is waited to carry out the adjustment of slurry viscosity.But when adjusting viscosity, addition is avoided with the dispersibility for making catalytic metal
The aqueous slkali of the tendency of decline.The supporter for being coated with mixed slurry is preferably dried before calcination.Drying temperature is preferably
90~200 DEG C.
Invention effect
For the exhaust gas purifying catalyst of the present invention while using the characteristic of a variety of catalytic metals, catalytic performance is especially excellent
It is good.
Description of the drawings
Fig. 1 is the EPMA analysis charts of the exhaust gas purifying catalyst in first embodiment.
Specific embodiment
The preferred forms in the present invention are illustrated below.
First embodiment：
It will be as the activated alumina of inorganic oxide (La doped gama-alumina) 100g, Ceria-zirconia composite oxygen
(CeZrLaY, zirconium oxide/cerium oxide ratio is 65/35) 60g and barium acetate (more than 99% purity) 7.0g are added to acetic acid to compound
In the mixed solution of 1.8g and pure water 0.17L, crush and mix using alumina lap machine, prepare carrier paste.Adding
In the case of adding zirconates, mixed nitrate oxygen zirconium (more than 99.0% purity) etc. is added in the carrier paste, then addition mixing
Palladium nitrate (Tianzhonggui Metal Industrial Co., Ltd's system) 8.3g and rhodium nitrate (Tianzhonggui Metal Industrial Co., Ltd's system) 1.7g, system
Standby mixed slurry.The pH of the slurry is about 4.4.Acetic acid, water are added in the slurry to adjust viscosity, and be coated on support
On body (cordierite integral material (モ ノ リ ス), volume 1L, hole count 600cpsi, wall thickness 4.3mil).Described above mixed
Close slurry prepare after and the stage until being applied on supporter, be not added with aqueous slkali.After being dried 30 minutes at 95 DEG C,
It is calcined 2 hours at 500 DEG C, obtains exhaust gas purifying catalyst (experiment No.1-2).
As described in Table 1, for being not added with the catalyst (experiment No.1-1) of barium salt and zirconates, changing adding for zirconates
The catalyst (experiment No.1-3~1-5) of dosage replaces urging for zirconyl nitrate using zirconium acetate, zirconium hydroxide, zirconia sol
Agent (experiment No.1-6~1-8), is manufactured also by method similar to the above.In addition, also manufacture comprising zirconyl nitrate,
And the catalyst (experiment No.1-9) of barium acetate is replaced using barium sulfate as barium salt.
[table 1]
The additive amount of ※ Ba salt and Zr salt is the ratio after oxide conversion.
About the catalyst obtained in above-mentioned, zirconium/cerium concentration ratio in analysis of catalyst layer, to catalytic metal on carrier
Load condition be also confirmed.In addition, as catalytic performance, the exhaust gas purifying ability of CO, NO, HC are had rated.
For the catalyst of above-mentioned experiment No.1-3~1-5, urged using electron ray microanalyzer (EPMA) to analyze
Zirconium/cerium concentration ratio in agent layer.About electronbeam irradiation condition, be set as accelerating potential 20kV, irradiation electric current 1.0 ×
10-8A, to the every 0.2 μm of mobile electron ray in catalyst layer surface layer to the irradiation position of catalyst layer from supporter immediate vicinity
To carry out ray analysis.It is obtained from catalyst layer surface layer to the zirconium/cerium at the place that locates of the depth on 5~10 μm of side of support
Average (the X of concentration ratio1) and the locating to the depth of 5~10 μm of surface layer side from the interface of supporter and catalyst layer
Zirconium/the cerium concentration at place than average (X2).It is less than 10 to locate as catalysis using the X-ray intensity of Zr in this experiment
The most surface of oxidant layer.Obtained surface layer side zirconium/cerium ratio (X is obtained1) with supporting side zirconium/cerium ratio (X2The ratio between), as urging
Zirconium concentration ratio (the X of agent layer surface layer side and support side1/X2).It will be shown in Figure 1 about the EPMA measurement results of No.1-5.
[table 2]
The additive amount of ※ Zr salt is the ratio after oxide conversion.
From Fig. 1, table 2 it has been confirmed that addition Zr salt and in the catalyst that manufactures, the Zr/Ce high near catalyst layer surface layer
In the near interface with supporter.
Then, confirm based on having no added Ba salt and Zr salt, catalytic metal to the load condition of carrier.The validation test
In, in the process of each catalyst of manufacture experiment No.1-1,1-2,1-9, use the mixed slurry after addition catalytic metal salt.
Specifically, for obtained from adding and carrying out filter filtering after the mixed slurry after palladium nitrate and rhodium nitrate centrifuges
Supernatant analyzes the concentration of noble metal (Pd and Rh) contained in liquid using high-frequency induction coupled plasma method (ICP).By
The ratio being fixed in the noble metal being added in slurry on inorganic oxide carrier is obtained in precious metal concentration in supernatant.
The above results are the mixed slurries in the manufacturing process for the catalyst (experiment No.1-1) for being not added with zirconates and barium salt
In, it is 87% fixed to the palladium on carrier and the ratio of rhodium.In contrast, it is added to the catalyst (experiment No.1-2) of barium salt
In, the ratio of fixed palladium and rhodium is 70%.In addition, it is added to the catalyst (experiment No.1-9) of both zirconates and barium salt
In, almost 100% palladium and rhodium are all fixed.
Then, for the catalyst of above experiment No.1-1~1-9, evaluation exhaust-gas purifying performance (T50).Performance evaluation
In, use the catalyst formed from supporter with cylindric punching core material.Be punched core material after catalyst performance evaluation it
Before, use the degradation treatment of atmosphere furnace progress 10 hours at 900 DEG C.About the reaction gas of performance evaluation, start to simulate
Machine exhaust gas, uses CO210%th, CO 0.77%, H20.2%th, C3H8 100ppm、C3H6 300ppm、NO800ppm、O2
0.4%th, H2O 10.0% is used as rich gas, uses CO210%th, CO 0.77%, H20.2%th, C3H8 100ppm、C3H6
300ppm、NO 800ppm、O20.4%th, H2O 10.0% is used as lean gas.The surplus of any atmosphere gas is N2.To catalyst
The reaction gas of supply was with 90000 hours-1Space velocity (SV) every 1 second continuously switch rich gas/lean gas.Make catalyst
Inlet temperature from 100 to 600 DEG C in the temperature reaction experiment of 40 DEG C/min of raising temperature, analysis of catalyst entrance and to go out
The reaction gas composition of mouth measures the purifying rate of carbon monoxide, hydrocarbon, nitrogen oxides.Purifying rate is reached 50%
Temperature is as T50, evaluate detergent power.T50It is lower, represent that the detergent power of catalyst is higher.
[table 3]
The additive amount weight % of ※ Ba salt and Zr salt is the ratio after oxide conversion
It will be apparent from the above that the T of the catalyst (experiment No.1-3~1-9) containing zirconates50It is low, any in CO, NO, HC
High catalytic activity is all shown in terms of purifying property.In addition, when containing both barium and zirconium oxide (experiment No.1-9), T50It is special
It is not low, show good catalytic activity.
It will be apparent from the above that the catalyst of zirconates is added to compared with the catalyst for being not added with zirconates, fixed on carrier
The amount of catalytic metal is more, and catalytic activity is better.It is added in the catalyst of both barium and zirconium oxide, used catalysis
Metal is nearly all fixed, and catalytic activity is also especially high.
Second embodiment：
Catalyst is manufactured using the barium sulfate of the grain size shown in table 4 below.Other manufacturing conditions, performance evaluation by with
First embodiment same method carries out.
[table 4]
The additive amount weight % of ※ Ba salt and Zr salt is the ratio after oxide conversion.
It will be apparent from the above that barium compound grain size for 0.01 μm less than 2 μm when, T50It is especially low, it shows good
Good catalytic activity.
Third embodiment：
The dispersion degree of the catalytic metal in catalyst layer is evaluated by CO absorption methods.In addition, after to carrying out degradation treatment
Catalyst also evaluated.
Catalyst is manufactured using the barium salt shown in table 5 below and zirconates.It tests in No.3-1, is added in carrier paste
After palladium nitrate and rhodium nitrate, addition TEAH makes pH rise to 7.0 as aqueous slkali.For testing the catalysis of No.3-3~3-5
Agent after catalyst is manufactured, carries out the degradation treatment of 10 hours at 950 DEG C.Other catalyst manufacturing conditions are implemented with first
Mode similarly manufactures catalyst.
For the catalyst obtained in above, the unit dispersion degree of catalytic metal peace is measured using CO Pulse adsorptions method
Equal grain size.Specifically, catalyst is kept for 15 minutes in oxygen atmosphere at 400 DEG C, then also 400 in hydrogen atmosphere
DEG C keep 15 minutes, after 50 DEG C are then cooled in helium atmosphere, pass through CO impulse methods measure CO adsorbances.Pass through the survey
It is fixed, the atomicity for the catalytic metal for being exposed to catalyst layer surface can be measured.Moreover, the expression of unit dispersion degree is supported on carrier
On catalytic metal amount in be exposed to catalyst layer surface amount ratio (%), calculated by CO adsorbances.Unit point
Divergence is bigger, then the surface area for exposing the part of catalytic metal in catalyst layer surface is bigger therefore readily available functional
Catalyst.In addition, from the surface area of the catalytic metal calculated according to CO adsorbances and the shape of catalytic metal is assumed to ball
Shape calculates average grain diameter.
[table 5]
※1:Adjusted using the pH of aqueous slkali (TEAH).
※2:The additive amount weight % of Ba salt and Zr salt is the ratio after oxide conversion.
※3:It tests in No.3-3, the aggregation of catalyst metals is notable, and the C0 adsorbances based on CO impulse methods are few, therefore
Fail to detect.
Never it from the point of view of the catalyst (experiment No.3-1,3-2) for carrying out degradation treatment, adds zirconates and aqueous slkali is not used
Catalyst (experiment No.3-2), compared with the catalyst (experiment No.3-1) after using aqueous slkali adjustment pH, the list of catalytic metal
Position dispersion degree higher, average grain diameter also smaller.Think in the catalyst after addition aqueous slkali, catalytic metal is with the shape of hydroxide
Formula is settled, therefore big grain size has occurred in catalytic metal.
About the catalyst (experiment No.3-3~3-5) after carrying out 10 hours degradation treatments at 900 DEG C, it is being not added with zirconates
Catalyst (experiment No.3-3) in, observe the large-scale aggregating of catalytic metal, the dispersion using CO impulse methods can not be carried out
The calculating of degree and grain size.In contrast, the catalyst (experiment No.3-4,3-5) of zirconates is added to, with not carrying out degradation treatment
Catalyst is compared, although observing the decline of dispersion degree and the increase of grain size, compared with the catalyst for being not added with zirconates, and catalysis
The aggregation of metal is inhibited.Therefore, for the catalyst for being added to zirconates, even if in use due to catalyst etc.
And make in the case that catalyst deteriorates, can also expect to inhibit the effect of the aggregation of catalytic metal.
Industrial availability
In accordance with the invention it is possible to it provides as the catalytic performance of exhaust gas purifying catalyst is high, the also low catalysis of manufacture cost
Agent.The exhaust gas purifying catalyst of the present invention is particularly suitable as three-way catalyst.
Claims (13)
1. a kind of exhaust gas purifying catalyst, the waste gas purification catalysis formed to form single catalyst layer on supporter
Agent, wherein,
The catalyst layer be by least any one inorganic oxide formed in aluminium oxide, cerium oxide, zirconium oxide with
The supported on carriers that Ceria-zirconia composite oxides mix has the catalyst layer of palladium and rhodium,
Also, the zirconium concentration (S on the surface of the catalyst layerZr) and cerium concentration (SCe) the ratio between (SZr/SCe) relative to catalyst layer
The interface with supporter zirconium concentration (CZr) and cerium concentration (CCe) the ratio between (CZr/CCe) for 1.05~6.0, the zirconium concentration with
The ratio between cerium concentration is measured to obtain by electron ray microanalyzer.
2. exhaust gas purifying catalyst as described in claim 1, wherein, catalyst layer also contains insoluble barium compound.
3. exhaust gas purifying catalyst as claimed in claim 2, wherein, barium compound is included in barium sulfate, barium carbonate, barium monoxide
Any one.
4. exhaust gas purifying catalyst as claimed in claim 2 or claim 3, wherein, the grain size of barium compound is for 0.01 μm or more and small
In 2.0 μm.
5. a kind of manufacturing method of exhaust gas purifying catalyst is catalyzed for waste gas purification according to any one of claims 1 to 4
The manufacturing method of agent, the manufacturing method include：
Addition palladium salt and rhodium salt in the carrier paste for forming inorganic oxide and the suspension of Ceria-zirconia composite oxides
And prepare as catalyst layer precursor mixed slurry process and
The process that the mixed slurry is coated on supporter and forms single-layer catalyst precursor layer,
Contain zirconium compounds in the carrier paste in the stage of the addition palladium salt and rhodium salt of the process for preparing mixed slurry.
6. manufacturing method as claimed in claim 5, wherein, in the addition palladium salt for the process for preparing mixed slurry and the rank of rhodium salt
Also contain insoluble barium compound in the carrier paste of section.
7. manufacturing method as claimed in claim 6, wherein, insoluble barium compound is barium sulfate or barium carbonate.
8. manufacturing method as claimed in claims 6 or 7, wherein, it is converted into oxygen relative to by whole ingredients in catalyst layer
The quality of compound, the additive amount of insoluble barium compound are calculated as 1.0~10 mass % to be converted into the quality of barium monoxide.
9. the manufacturing method as described in any one of claim 5~7, wherein, zirconium compounds is zirconyl nitrate, zirconium acetate, oxygen
Change more than any one in zirconium colloidal sol.
10. the manufacturing method as described in any one of claim 5~7, wherein, relative to by whole ingredients in catalyst layer
The quality of oxide is converted into, the additive amount of zirconium compounds is calculated as 0.5~5.0 mass % to be converted into the quality of zirconium oxide.
11. manufacturing method as claimed in claims 6 or 7, wherein, insoluble barium compound and Ceria-zirconia is compound
Oxide and inorganic oxide carry out after being mixed together slurried preparing carrier paste.
12. the manufacturing method as described in any one of claim 5~7, wherein, by Ceria-zirconia composite oxides
Mixed with inorganic oxide and carry out it is slurried and after preparing carrier paste, zirconium compounds is carried out before the addition of palladium salt and rhodium salt
Addition.
13. the manufacturing method as described in any one of claim 5~7, wherein, after the formation process of catalyst precarsor layer,
Supporter is calcined at 400~700 DEG C and forms catalyst layer.
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| JP2013249137A JP5777690B2 (en) | 2013-12-02 | 2013-12-02 | Exhaust gas purification catalyst and method for producing the same |
| JP2013-249137 | 2013-12-02 | ||
| PCT/JP2014/081205 WO2015083590A1 (en) | 2013-12-02 | 2014-11-26 | Exhaust-gas purifying catalyst and method for producing same |
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| EP3409355B1 (en) * | 2016-01-28 | 2020-04-15 | Cataler Corporation | Pd-supporting zr-based composite oxide |
| EP3581269B1 (en) * | 2017-04-11 | 2022-09-28 | Cataler Corporation | Catalyst for exhaust gas purification and method of preparation |
| WO2019131176A1 (en) * | 2017-12-28 | 2019-07-04 | ユミコア日本触媒株式会社 | Hydrogen production catalyst and exhaust gas purification catalyst using same |
| CN108993560A (en) * | 2018-07-25 | 2018-12-14 | 昆明贵研催化剂有限责任公司 | A kind of water resistant, high temperature resistant methane oxidation catalyst and preparation method thereof |
| CN112675845B (en) * | 2020-12-28 | 2022-03-29 | 四川大学 | Pd-Rh single-coating catalyst for purifying tail gas of natural gas vehicle and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4965243A (en) * | 1987-08-28 | 1990-10-23 | Engelhard Corporation | Process for producing a catalyst for purifying exhaust gases from internal combustion engines |
| CN1262144A (en) * | 1998-10-13 | 2000-08-09 | 底古萨－胡尔斯股份公司 | Nitrogen oxide storing catalyst |
| EP1053779A1 (en) * | 1997-11-20 | 2000-11-22 | Daihatsu Motor Co., Ltd. | Catalytic converter for cleaning exhaust gas |
| CN1854474A (en) * | 2005-04-27 | 2006-11-01 | 马自达汽车股份有限公司 | Diesel particulate filter |
| CN101284233A (en) * | 2007-04-12 | 2008-10-15 | 日产自动车株式会社 | Exhaust gas purifying catalyst and method of producing the same |
| CN101716535A (en) * | 2008-10-08 | 2010-06-02 | 三井金属矿业株式会社 | Method for preparing waste gas purifying catalyst |
| CN101820997A (en) * | 2007-08-09 | 2010-09-01 | 巴斯夫催化剂公司 | Catalyst compositions |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK0428753T3 (en) * | 1989-06-09 | 1995-07-03 | N E Chemcat Corp | Catalytic converter for cleaning exhaust gas with excellent heat resistance and process for its preparation |
| JP3235640B2 (en) * | 1995-11-09 | 2001-12-04 | 株式会社アイシーティー | Internal combustion engine exhaust gas purification catalyst |
| US20020128151A1 (en) * | 1998-05-01 | 2002-09-12 | Michael P. Galligan | Catalyst members having electric arc sprayed substrates and methods of making the same |
| JP4633509B2 (en) * | 2005-03-24 | 2011-02-16 | マツダ株式会社 | Exhaust gas purification catalyst |
| RU2457901C2 (en) * | 2008-03-19 | 2012-08-10 | АйСиТи КО., ЛТД. | Catalyst for cleaning internal combustion engine exhaust gas and method of cleaning exhaust gas using said catalyst |
-
2013
- 2013-12-02 JP JP2013249137A patent/JP5777690B2/en active Active
-
2014
- 2014-11-26 CN CN201480066003.3A patent/CN105792929B/en active Active
- 2014-11-26 WO PCT/JP2014/081205 patent/WO2015083590A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4965243A (en) * | 1987-08-28 | 1990-10-23 | Engelhard Corporation | Process for producing a catalyst for purifying exhaust gases from internal combustion engines |
| EP1053779A1 (en) * | 1997-11-20 | 2000-11-22 | Daihatsu Motor Co., Ltd. | Catalytic converter for cleaning exhaust gas |
| CN1262144A (en) * | 1998-10-13 | 2000-08-09 | 底古萨－胡尔斯股份公司 | Nitrogen oxide storing catalyst |
| CN1854474A (en) * | 2005-04-27 | 2006-11-01 | 马自达汽车股份有限公司 | Diesel particulate filter |
| CN101284233A (en) * | 2007-04-12 | 2008-10-15 | 日产自动车株式会社 | Exhaust gas purifying catalyst and method of producing the same |
| CN101820997A (en) * | 2007-08-09 | 2010-09-01 | 巴斯夫催化剂公司 | Catalyst compositions |
| CN101716535A (en) * | 2008-10-08 | 2010-06-02 | 三井金属矿业株式会社 | Method for preparing waste gas purifying catalyst |
Non-Patent Citations (3)
| Title |
|---|
| "Metal-promoter interface in Pd/(Ce,Zr)O-x/Al2O3 catalysts: effect of thermal aging";Iglesias-Juez 等;《JOURNAL OF CATALYSIS》;20040101;第221卷(第1期);第148-161页 * |
| "The effect of Nd on the properties of ceria-zirconia solid solution and the catalytic performance of its supported Pd-only three-way catalyst for gasoline engine exhaust reduction";Wang, QY 等;《JOURNAL OF HAZARDOUS MATERIALS》;20110515;第189卷(第1-2期);第150-157页 * |
| "天然气汽车尾气净化催化剂的制备和性能初探";赵彬;《中国优秀硕士学位论文全文数据库（工程科技Ⅰ辑）》;20050131(第1期);B016-384 * |
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| WO2015083590A1 (en) | 2015-06-11 |
| JP2015104715A (en) | 2015-06-08 |
| CN105792929A (en) | 2016-07-20 |
| JP5777690B2 (en) | 2015-09-09 |
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