CN110801832A - Gasoline engine tail gas purification three-effect catalyst meeting national emission standard - Google Patents
Gasoline engine tail gas purification three-effect catalyst meeting national emission standard Download PDFInfo
- Publication number
- CN110801832A CN110801832A CN201911005774.2A CN201911005774A CN110801832A CN 110801832 A CN110801832 A CN 110801832A CN 201911005774 A CN201911005774 A CN 201911005774A CN 110801832 A CN110801832 A CN 110801832A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- tail gas
- layer
- gasoline engine
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 238000000746 purification Methods 0.000 title abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000012041 precatalyst Substances 0.000 claims abstract description 22
- 239000010970 precious metal Substances 0.000 claims abstract description 18
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 13
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- 239000011148 porous material Substances 0.000 claims description 48
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 26
- 229910000510 noble metal Inorganic materials 0.000 claims description 24
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 15
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 15
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 11
- 229910052703 rhodium Inorganic materials 0.000 claims description 9
- 239000010948 rhodium Substances 0.000 claims description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 abstract description 5
- 230000006872 improvement Effects 0.000 abstract 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 40
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 20
- 239000004615 ingredient Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 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 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- 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
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/012—Diesel engines and lean burn gasoline engines
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
A gasoline engine tail gas purification three-effect catalyst meeting the national six-emission standard comprises a main catalyst and a pre-catalyst, wherein the main components of the pre-catalyst are modified alumina, cerium/zirconium mixed oxide and precious metal active components, the pre-catalyst comprises a base layer I, a middle layer II and an outer layer III, each layer is provided with a front region and a rear region, the front region is an upstream region with more precious metal active components, the rear region is a downstream region with lower precious metal active components than the front region, the main catalyst comprises a base layer A, a middle layer B and an outer layer C, the precious metal active component content of the middle layer is higher than that of the base layer A and the outer layer C, the precious metal active component content in the main catalyst is lower than that of the pre-catalyst, the effective utilization of the precious metal active components and the remarkable improvement of the thermal stability of the catalyst are realized, and the light-off temperature, the ignition temperature and the ignition temperature of the catalyst are reduced, The durability of the catalyst is improved.
Description
Technical Field
The invention belongs to the technical field of gasoline engine tail gas purification, and particularly relates to a gasoline engine tail gas purification three-way catalyst meeting the national emission standard.
Background
The method is the most effective mode for treating the tail gas of the gasoline engine, namely 12 and 23 days in 2016, GB18352.6-2016 (national ministry of environmental protection) publication GB18352.6-2016 (limit for emission of pollutants in light-duty automobiles) and a measurement method (sixth stage in China), from 7 and 1 days in 2020, all light-duty automobiles sold and registered should meet the standard requirement, wherein a type I test should meet the 6a limit requirement; since 7/1/2023, all light vehicles sold and registered should meet the standards, with the type i test meeting the 6b limit.
In consideration of long development period and high development cost of new vehicles, a plurality of vehicle enterprises select to directly develop vehicle types meeting the emission standard of the national Liu-b; this also means that a matched gasoline engine exhaust purifier must employ a three-way catalyst that meets the emissions standards of the national Liuba.
National emission standards of six allow for a significant reduction in emission values for pollutants relative to national emission standards of five, which means that the matched catalyst needs to have higher conversion efficiency and lower light-off temperature; the national emission standard adopts more transient WLTC circulation, and a matched catalyst has more excellent oxygen storage and release performance; and the regulation of the national six-emission standard on the use aging of the catalyst is 20 kilometers, and higher requirements are put on the thermal stability of the catalyst.
The document with the grant number CN104334255B discloses a three-way catalyst system, which comprises a first three-way catalyst on an inert catalyst support and a second three-way catalyst located upstream of the first three-way catalyst, wherein the first three-way catalyst is a double-layer catalyst comprising a first layer and a second layer, the first layer comprises active alumina, cerium/zirconium mixed oxide and palladium, and the second layer comprises active alumina and rhodium and does not contain cerium and cerium-containing materials.
Disclosure of Invention
The invention aims to provide a gasoline engine tail gas purification three-way catalyst meeting the national emission standard, which realizes high dispersion of noble metal active components according to different types and concentrations of noble metals adsorbed and deposited in different subareas so as to integrally improve the high-temperature thermal stability of the catalyst.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a gasoline engine tail gas purification three-effect catalyst meeting the national emission standard comprises a main catalyst and a pre-catalyst, wherein the main components of the pre-catalyst are modified alumina, cerium/zirconium mixed oxide and precious metal active components, the pre-catalyst comprises a base layer I, a middle layer II and an outer layer III, each layer is provided with a front region and a rear region, the front region is an upstream region with more precious metal active components, and the rear region is a downstream region with lower precious metal active components than the front region.
Further, the main catalyst comprises a base layer A, an intermediate layer B and an outer layer C, the content of the noble metal active component in the intermediate layer is larger than that of the base layer A and the outer layer C, and the content of the noble metal active component in the main catalyst is lower than that in the pre-catalyst.
In the design of the scheme, a double-layer catalyst comprising a main catalyst and a pre-catalyst is arranged, in order to improve the dispersion degree and the effective utilization of the active components of the precious metal in the catalyst, the pre-catalyst which plays the main catalytic action is divided into at least six areas from top to bottom and from upstream to downstream, through the layout mode, the proportion of modified oxides and rare earth composite oxides among different levels and different areas can be adjusted, so that the type and the concentration of the precious metal are adjusted, the content of the active components of the precious metal is lower than that of the pre-catalyst according to the flow direction of tail gas, the content of the active components of the precious metal is gradually reduced from upstream to downstream, and the characteristics that the content of the basic layer, the middle layer and the middle layer of the outer layer is reduced towards two sides are distributed, so that the effective utilization of the active components of the precious metal and the remarkable improvement of the thermal, The durability of the catalyst is improved.
Preferably, the cerium/zirconium mixed oxide comprises: ce1: the weight ratio of the cerium oxide to the zirconium oxide is 0.8-1.2; ce2: the weight ratio of the cerium oxide to the zirconium oxide is 0.6-0.8.
Further, Ce1Or Ce2The specific surface area of (A) is 70-100 m2Per g, pore volume of 0.5-0.6 cm3The pore diameter is 10-100 nm.
Further preferably, Ce1Or Ce2Aging at 1000 deg.C to specific surface area of 40m or more2G, aging at 1100 deg.C, and specific surface area of not less than 20m2/g。
In the design of the scheme, through repeated tests, the cerium/zirconium mixed oxide with the parameters has good high-temperature sintering resistance, excellent oxygen hole concentration and oxygen storage capacity, and can reduce the ignition temperature of the three-way catalyst.
Preferably, the modified alumina is a rare earth modified alumina material, the rare earth elements comprise lanthanum, neodymium and yttrium, and the specific surface area of the rare earth elements is 160-260 m2Per g, pore volume of 0.3-0.8 cm3The pore diameter is 0.5-100 nm.
More preferably, the specific surface area of the modified alumina is 180-200 m2Per g, pore volume of 0.5-0.8 cm3The pore diameter is 4-40 nm, and the specific surface area is more than or equal to 40m after aging at 1200 DEG C2/g。
The stability of the overall catalyst depends to a large extent on the surface area of the coating in which w (gamma-Al) is present and the adhesion of the coating to the support2O3) Usually more than 90%, so that gamma-Al2O3The stability of the solution is critical, and in the design of the solution, the solution is pure gamma-Al2O3For preventing gamma-Al at high temperature2O3To α -Al2O3Oxides of lanthanum, neodymium, yttrium elements converted as stabilizers and against gamma-Al2O3The specific surface area limit value of the catalyst is within a higher standard, the modified alumina with good stability and larger specific surface area under high temperature condition is obtained, the noble metal active component is favorably highly dispersed on a base layer consisting of the modified alumina and the cerium/zirconium mixed oxide, and the utilization rate of the noble metal active component is improved.
Preferably, the noble metal active component comprises one or more of platinum, palladium, rhodium.
Platinum or palladium is selected and mainly used for converting CO and HC, and has the advantages of low price, rich resources, good heat resistance and the like; rh is the main component for controlling the content of nitrogen oxide and can effectively treat NOxAnd has good durability and is not easy to be poisoned.
Preferably, oxides of lanthanum, neodymium, yttrium and praseodymium are contained in the cerium/zirconium mixed oxide for improving the performance.
The invention has the following beneficial effects:
in the design of the scheme, the catalyst comprises a plurality of catalyst subareas with different precious metal active components and concentrations, each subarea comprises an aluminum oxide material with large surface area and high thermal stability, a rare earth composite oxide material with excellent oxygen storage and storage performance and other auxiliary agents, and the catalyst is coated on a common honeycomb ceramic carrier, so that the high dispersion and thermal stability of the precious metal active components on the subareas can be realized, and the catalyst is applied to an exhaust purifier, has lower ignition temperature, improved oxygen storage and storage performance and high-temperature thermal stability, and enables the automobile exhaust emission to meet the requirements of the emission standard of the national Liub.
Detailed Description
Examples
The three-effect catalyst for purifying the tail gas of the gasoline engine comprises a main catalyst coated on a honeycomb ceramic carrier and a pre-catalyst which is applied to the main catalyst and is in direct contact with the exhaust to be purified, wherein the main catalyst comprises a base layer A, a middle layer B and an outer layer C, and the specific mixture ratio is as follows:
base layer A: the base layer was composed of a catalyst containing 3.5% by weight of lanthanum oxide and having a specific surface area of 180 m2Per g, pore volume 0.5m3Alumina with a pore diameter of 40nm and/gContaining 1.0wt% of yttrium oxide and having a specific surface area of 70 m2Pore volume of 0.5 cm/g3Ce of 100nm pore diameter/g1Is mixed to prepare, wherein, Ce1Medium cerium oxide: zirconium oxide is 1:1, palladium nitrate is used as a noble metal precursor and is deposited on the base layer;
the composition of the base layer a is: 80g/L lanthanum oxide stabilized alumina, 60g/L Ce mixed yttria10.3g/L palladium (on all ingredients).
An intermediate layer B: the base layer was composed of a catalyst containing 3.0wt% of lanthanum oxide and having a specific surface area of 190 m2Per g, pore volume 0.6m3Alumina with a pore diameter of 20nm and a specific surface area of 80 m containing 1.0 wt.% of praseodymium oxide2Pore volume of 0.6 cm/g3Ce of 50nm pore size/g1Is mixed to prepare, wherein, Ce1Medium cerium oxide: zirconium oxide is 4:5, palladium nitrate and rhodium nitrate are used as noble metal precursors and are deposited on the base layer;
the composition of the intermediate layer B is: 70g/L lanthanum oxide stabilized alumina, 35g/L mixed praseodymium oxide Ce10.3g/L palladium (on all ingredients), 0.15g/L rhodium (on all ingredients).
An outer layer C: the base layer is composed of a material containing 2.5wt% of lanthanum oxide and having a specific surface area of 200m2Per g, pore volume 0.8m3Alumina with a pore diameter of 4 nm and a specific surface area of 100m containing 1.0 wt.% of neodymium oxide2Per g, pore volume 0.55cm3Ce of 10nm pore diameter/g1Is mixed to prepare, wherein, Ce1Medium cerium oxide: zirconium oxide is 6:5, palladium nitrate and rhodium nitrate are used as noble metal precursors and are deposited on the base layer;
the composition of the outer layer C is: 75g/L lanthanum oxide stabilized alumina, 75g/L mixed neodymium oxide Ce10.2g/L palladium (on all ingredients), 0.05g/L rhodium (on all ingredients).
The precatalyst comprises: the base layer I front area, the base layer I back area, the middle layer II front area, the middle layer II back area, the outer layer III front area and the outer layer III back area are specifically proportioned as follows:
base layer i front zone: base ofThe layer is composed of a layer containing 3.0wt% of lanthanum oxide and having a specific surface area of 200m2Per g, pore volume 0.6m3Alumina with a pore diameter of 20nm and a specific surface area of 95 m containing 0.5 wt.% of neodymium oxide2Pore volume of 0.5 cm/g3Ce of 20nm pore diameter/g1Is mixed to prepare, wherein, Ce1Medium cerium oxide: zirconium oxide is 6:5, palladium nitrate is used as a noble metal precursor and is deposited on the base layer;
the composition of the base layer I front region is: 80g/L lanthanum oxide stabilized alumina, 60g/L mixed neodymium oxide Ce10.5g/L palladium (on all ingredients).
Base layer i rear zone: the base layer was composed of a catalyst containing 3.0wt% of lanthanum oxide and having a specific surface area of 200m2Per g, pore volume 0.8m3Alumina with a pore diameter of 20nm and a specific surface area of 100m containing 0.5 wt.% of neodymium oxide2Pore volume of 0.6 cm/g3Ce of 10nm pore diameter/g1Is mixed to prepare, wherein, Ce1Medium cerium oxide: zirconium oxide is 4:5, palladium nitrate is used as a noble metal precursor and is deposited on the base layer;
the composition of the base layer I back zone is: 80g/L lanthanum oxide stabilized alumina, 40g/L mixed neodymium oxide Ce10.3g/L palladium (on all ingredients).
Front region of middle layer II: the base layer was composed of a catalyst containing 3.0wt% of lanthanum oxide and having a specific surface area of 200m2Per g, pore volume 0.8m3Alumina with a pore diameter of 20nm and a specific surface area of 100m containing 1.5 wt.% of neodymium oxide2Pore volume of 0.6 cm/g3Ce of 10nm pore diameter/g1Is mixed to prepare, wherein, Ce1Medium cerium oxide: zirconium oxide is 1:1, palladium nitrate and rhodium nitrate are used as noble metal precursors and are deposited on the base layer;
the composition of the front region of the middle layer II is: 80g/L lanthanum oxide stabilized alumina, 20g/L mixed neodymium oxide Ce10.85g/L palladium (on all ingredients), 0.06g/L rhodium (on all ingredients).
Zone after intermediate layer ii: the base layer was composed of a catalyst containing 3.0wt% of lanthanum oxide and having a specific surface area of 200m2Per g, pore volume 0.8m3Alumina with a pore diameter of 20nm and a specific surface area of 100m containing 1.5 wt.% of neodymium oxide2Pore volume of 0.6 cm/g3Ce of 10nm pore diameter/g1Is mixed to prepare, wherein, Ce1Medium cerium oxide: zirconium oxide is 1:1, palladium nitrate and rhodium nitrate are used as noble metal precursors and are deposited on the base layer;
the composition of the zone behind the intermediate layer II is: 80g/L lanthanum oxide stabilized alumina, 20g/L mixed neodymium oxide Ce10.75g/L palladium (on all ingredients), 0.05g/L rhodium (on all ingredients).
Front region of outer layer III: the base layer is composed of a material containing 2.5wt% of lanthanum oxide and having a specific surface area of 200m2Per g, pore volume 0.8m3Alumina with a pore diameter of 4 nm and a specific surface area of 100m containing 1.0 wt.% of lanthanum oxide2Per g, pore volume 0.55cm3Ce of 10nm pore diameter/g1And Ce2Is mixed to prepare, wherein, Ce1Medium cerium oxide: zirconia is 6:5, Ce2Medium cerium oxide: zirconium oxide is 4:5, palladium nitrate and rhodium nitrate are used as noble metal precursors and are deposited on the base layer;
the composition of the pro-region of outer layer III was: alumina stabilized by 80g/L lanthana, Ce of 60g/L mixed lanthana160g/L of mixed lanthanum oxide Ce20.375g/L palladium (on all ingredients), 0.025g/L rhodium (on all ingredients).
Outer zone III rear zone: the base layer is composed of a material containing 2.5wt% of lanthanum oxide and having a specific surface area of 200m2Per g, pore volume 0.8m3Alumina with a pore diameter of 4 nm and containing 1.0 wt.% of yttrium oxide and having a specific surface area of 100m2Per g, pore volume 0.55cm3Ce of 10nm pore diameter/g1And Ce2Is mixed to prepare, wherein, Ce1Medium cerium oxide: zirconia is 6:5, Ce2Medium cerium oxide: zirconium oxide is 4:5, palladium nitrate and rhodium nitrate are used as noble metal precursors and are deposited on the base layer;
the composition of the outer zone III rear section is: 80g/L lanthanum oxide stabilized alumina, 70g/L Ce mixed yttria150g/L of a mixtureCe of yttria20.0385g/L palladium (on all ingredients), 0.0125g/L rhodium (on all ingredients).
Coating a pre-catalyst and a main catalyst on a honeycomb ceramic carrier, packaging the honeycomb ceramic carrier into a purifier, and mounting the purifier on an engine bench to test the ignition temperature T50, wherein HC is less than or equal to 280oC，CO≤270oC，NOx≤270oC. After simulating 20 kilometres of durable aging, the test ignition temperature T50 is that HC is less than or equal to 390oC，CO≤390oC，NOx≤390oC. After being installed on the whole vehicle (matched with a 1.5L engine), the emission results of the I-type test of the whole vehicle are shown in the following table:
test result of vehicle emission type I and catalyst conversion efficiency
After aging, the finished vehicle type I test emission results are shown in the following table:
from the above data, it can be seen that the system of this example is applicable to THC, NMHC and NOxThe purification effect of CO is good, and the purification effect after aging also meets the requirement of the emission standard of the national Liu B.
Comparative example
Main catalyst: the difference from the embodiment 1 is that the main catalyst is not layered, and the content of the noble metal is the total amount of the noble metal in the main catalyst in the embodiment 1;
pre-catalyst: the difference from the example 1 is that the precatalyst is not layered and zoned, and the content of the noble metal is the total amount of the noble metal in the precatalyst in the example 1;
repeatedly coating (repeating for at least 3 times) the main catalyst and the pre-catalyst on the honeycomb ceramic carrier, wherein the quality of the coating is the same as that in the embodiment 1, packaging the main catalyst and the pre-catalyst into a purifier, and mounting the purifier on an engine bench to test the ignition temperature T50, wherein HC is less than or equal to 290oC，CO≤290oC，NOx≤280oC. After simulating 20 kilometres of durable aging, testing the ignition temperature T50 and HC less than or equal to 420oC，CO≤420oC，NOx≤420oC. After being installed on the whole vehicle (matched with a 1.5L engine), the emission results of the I-type test of the whole vehicle are shown in the following table:
after aging, the finished vehicle type I test emission results are shown in the following table:
as is clear from the results of the examples and comparative examples, the results of the comparative examples were found to be for THC, NMHC and NOxThe purification effect of CO was not as good as that of the example, and the degradation of the purification effect after aging was significant, which proved that the thermal stability of the catalyst was not good, probably due to the poor dispersion of the noble metal active ingredient caused by the non-zoned precatalyst.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (10)
1. The three-way catalyst for purifying the tail gas of the gasoline engine as claimed in claim 1, which comprises a pre-catalyst, wherein the pre-catalyst comprises a base layer I containing modified alumina, cerium/zirconium mixed oxide and noble metal active component, and an intermediate layer II and an outer layer III having the same main components as the base layer I, the intermediate layer II and the outer layer III respectively comprise a front region and a rear region, and the content of the noble metal active component in the front region of each layer is greater than that in the rear region.
2. The three-way catalyst for purifying the tail gas of the gasoline engine as claimed in claim 1, which comprises a main catalyst, wherein the main catalyst comprises a base layer A containing modified alumina, cerium/zirconium mixed oxide and precious metal active components, and an intermediate layer B and an outer layer C which have the same main components as the base layer A, and the content of the precious metal active components in the intermediate layer B is greater than that in the base layer A or the outer layer C.
3. The three-way catalyst for purifying the tail gas of the gasoline engine as claimed in any one of claims 1 or 2, wherein the cerium/zirconium mixed oxide comprises:
Ce1: the mass ratio of the cerium oxide to the zirconium oxide is 0.8-1.2;
Ce2: the mass ratio of the cerium oxide to the zirconium oxide is 0.6-0.8.
4. The three-way catalyst for purifying tail gas of gasoline engines as claimed in claim 3, wherein the Ce is1Or Ce2The specific surface area of (A) is 70-100 m2Per g, pore volume of 0.5-0.6 cm3The pore diameter is 10-100 nm.
5. The three-way catalyst for purifying tail gas of gasoline engines as claimed in claim 4, wherein the Ce is1Or Ce2Aging at 1000 deg.C to specific surface area of 40m or more2G, aging at 1100 deg.C, and specific surface area of not less than 20m2/g。
6. The three-way catalyst for purifying the tail gas of the gasoline engine as claimed in any one of claims 1 or 2, wherein the specific surface area of the modified alumina is 160-260 m2Per g, pore volume of 0.3-0.8 cm3The pore diameter is 0.5-100 nm.
7. The three-way catalyst for purifying the tail gas of the gasoline engine as claimed in claim 6, wherein the specific surface area of the modified alumina is 180-200 m2Per g, pore volume of 0.5-0.8 cm3The pore diameter is 4-40 nm, and the specific surface area is more than or equal to 40m after aging at 1200 DEG C2/g。
8. The three-way catalyst for purifying the tail gas of the gasoline engine as claimed in claim 1, wherein the noble metal active component comprises one or more of platinum, palladium and rhodium.
9. The three-way catalyst for purifying the tail gas of the gasoline engine as claimed in claim 1, wherein the modified alumina is a rare earth modified alumina material, and the rare earth elements comprise lanthanum, neodymium and yttrium.
10. The three-way catalyst for purifying the tail gas of the gasoline engine as claimed in claim 1, wherein the cerium/zirconium mixed oxide contains oxides of lanthanum, neodymium, yttrium and praseodymium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911005774.2A CN110801832A (en) | 2019-10-22 | 2019-10-22 | Gasoline engine tail gas purification three-effect catalyst meeting national emission standard |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911005774.2A CN110801832A (en) | 2019-10-22 | 2019-10-22 | Gasoline engine tail gas purification three-effect catalyst meeting national emission standard |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110801832A true CN110801832A (en) | 2020-02-18 |
Family
ID=69488825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911005774.2A Pending CN110801832A (en) | 2019-10-22 | 2019-10-22 | Gasoline engine tail gas purification three-effect catalyst meeting national emission standard |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110801832A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112213109A (en) * | 2020-09-16 | 2021-01-12 | 哈尔滨东安汽车发动机制造有限公司 | Initial phase test method for variable valve timing system of engine |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0704241A1 (en) * | 1994-09-29 | 1996-04-03 | Corning Incorporated | Catalyst structure comprizing a cellular substrate and a layer of catalytically active material |
| KR100781670B1 (en) * | 2006-08-16 | 2007-12-03 | 희성촉매 주식회사 | Catalysts for internal combustion engine exhaust gas purification, containing no traces of rhodium or rhodium |
| CN101161337A (en) * | 2006-10-13 | 2008-04-16 | 比亚迪股份有限公司 | A ternary catalyst and its preparing method |
| CN101237933A (en) * | 2005-08-01 | 2008-08-06 | 株式会社卡特勒 | Catalyst for Exhaust Purification |
| CN101249438A (en) * | 2008-03-21 | 2008-08-27 | 无锡威孚环保催化剂有限公司 | Metal composite oxide material with three-level structure and preparation method thereof |
| CN102513165A (en) * | 2011-12-14 | 2012-06-27 | 刘碧兰 | Efficient method for coating tail gas clean-up three-way catalyst |
| CN102580733A (en) * | 2011-12-15 | 2012-07-18 | 无锡威孚环保催化剂有限公司 | Method for preparing Pd-only catalyst used for tail gas purification of universal minitype petrol engines |
| CN102979606A (en) * | 2012-11-23 | 2013-03-20 | 四川中自尾气净化有限公司 | Motorcycle tail gas catalytic converter and preparation method thereof |
| CN105536786A (en) * | 2015-12-15 | 2016-05-04 | 重庆海特汽车排气系统有限公司 | Ternary catalyst for purifying automobile exhaust |
| CN107923288A (en) * | 2015-06-24 | 2018-04-17 | 巴斯夫公司 | It is layered automobile catalyst composite material |
| CN108837829A (en) * | 2018-05-29 | 2018-11-20 | 无锡威孚环保催化剂有限公司 | A kind of layer-stepping natural gas vehicle three-way catalyst preparation method |
| CN108883406A (en) * | 2016-02-03 | 2018-11-23 | 巴斯夫公司 | Multi-layer catalyst composition for internal combustion engine |
| CN109261220A (en) * | 2018-09-28 | 2019-01-25 | 昆明贵研催化剂有限责任公司 | A kind of preparation method and application of non-homogeneous coating tai-gas clean-up catalyst |
-
2019
- 2019-10-22 CN CN201911005774.2A patent/CN110801832A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0704241A1 (en) * | 1994-09-29 | 1996-04-03 | Corning Incorporated | Catalyst structure comprizing a cellular substrate and a layer of catalytically active material |
| CN101237933A (en) * | 2005-08-01 | 2008-08-06 | 株式会社卡特勒 | Catalyst for Exhaust Purification |
| KR100781670B1 (en) * | 2006-08-16 | 2007-12-03 | 희성촉매 주식회사 | Catalysts for internal combustion engine exhaust gas purification, containing no traces of rhodium or rhodium |
| CN101161337A (en) * | 2006-10-13 | 2008-04-16 | 比亚迪股份有限公司 | A ternary catalyst and its preparing method |
| CN101249438A (en) * | 2008-03-21 | 2008-08-27 | 无锡威孚环保催化剂有限公司 | Metal composite oxide material with three-level structure and preparation method thereof |
| CN102513165A (en) * | 2011-12-14 | 2012-06-27 | 刘碧兰 | Efficient method for coating tail gas clean-up three-way catalyst |
| CN102580733A (en) * | 2011-12-15 | 2012-07-18 | 无锡威孚环保催化剂有限公司 | Method for preparing Pd-only catalyst used for tail gas purification of universal minitype petrol engines |
| CN102979606A (en) * | 2012-11-23 | 2013-03-20 | 四川中自尾气净化有限公司 | Motorcycle tail gas catalytic converter and preparation method thereof |
| CN107923288A (en) * | 2015-06-24 | 2018-04-17 | 巴斯夫公司 | It is layered automobile catalyst composite material |
| CN105536786A (en) * | 2015-12-15 | 2016-05-04 | 重庆海特汽车排气系统有限公司 | Ternary catalyst for purifying automobile exhaust |
| CN108883406A (en) * | 2016-02-03 | 2018-11-23 | 巴斯夫公司 | Multi-layer catalyst composition for internal combustion engine |
| CN108837829A (en) * | 2018-05-29 | 2018-11-20 | 无锡威孚环保催化剂有限公司 | A kind of layer-stepping natural gas vehicle three-way catalyst preparation method |
| CN109261220A (en) * | 2018-09-28 | 2019-01-25 | 昆明贵研催化剂有限责任公司 | A kind of preparation method and application of non-homogeneous coating tai-gas clean-up catalyst |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112213109A (en) * | 2020-09-16 | 2021-01-12 | 哈尔滨东安汽车发动机制造有限公司 | Initial phase test method for variable valve timing system of engine |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1969214B1 (en) | Exhaust system comprising zoned oxidation catalyst | |
| JP5322526B2 (en) | Honeycomb structure type catalyst for purifying exhaust gas discharged from automobile, method for manufacturing the same, and method for purifying exhaust gas using the catalyst | |
| US8227374B2 (en) | Exhaust gas purification catalyst | |
| JP6246192B2 (en) | Three-way catalyst system | |
| EP1793914B1 (en) | Catalyst for purifying exhaust gases | |
| KR20090045214A (en) | Ternary catalyst | |
| CN105492107B (en) | Catalytic converter | |
| EP3632537A1 (en) | Exhaust gas purification catalyst device | |
| EP2692436B1 (en) | Exhaust gas purification catalyst | |
| EP2047903A1 (en) | Catalyst for exhaust gas purification | |
| US20230256418A1 (en) | Three-way catalyst having low nh3 formation and preparation method therefor | |
| EP3730203A1 (en) | Exhaust gas purification catalyst | |
| CN110732320A (en) | diesel engine tail gas oxidation catalyst and preparation method and application thereof | |
| CN110801832A (en) | Gasoline engine tail gas purification three-effect catalyst meeting national emission standard | |
| CN110918092A (en) | Sectional catalyst and preparation method thereof | |
| CN110801834B (en) | Catalyst coating for purifying automobile exhaust and preparation method thereof | |
| CN110201666B (en) | Gasoline engine particle trapping catalyst and preparation method thereof | |
| JP7504252B1 (en) | Exhaust gas purification catalyst device and exhaust gas purification catalyst system | |
| CN110801833B (en) | Localized coating of automobile exhaust purification catalyst and preparation method thereof | |
| US20070123418A1 (en) | Catalyst composition containing gallium for purifying exhaust gases of internal combustion engine | |
| JP2025076169A (en) | Exhaust gas purification catalyst | |
| CN120079426A (en) | A GPF catalyst located on the chassis of an automobile to reduce ammonia emissions | |
| JPH09225306A (en) | Exhaust gas purification catalyst and method for producing the same | |
| Ichihara et al. | Recent Trends in the Application of Tri-Metal Emission Control Catalysts | |
| JPS6257651A (en) | Monolith catalyst for cleaning up of exhaust gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200218 |