CN113694924A - Platinum-rhodium/barium-based catalytic material, lean-burn nitrogen oxide catalyst and preparation method - Google Patents
Platinum-rhodium/barium-based catalytic material, lean-burn nitrogen oxide catalyst and preparation method Download PDFInfo
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- CN113694924A CN113694924A CN202110842341.3A CN202110842341A CN113694924A CN 113694924 A CN113694924 A CN 113694924A CN 202110842341 A CN202110842341 A CN 202110842341A CN 113694924 A CN113694924 A CN 113694924A
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- 239000000463 material Substances 0.000 title claims abstract description 127
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 114
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 229910052788 barium Inorganic materials 0.000 title claims abstract description 34
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000010948 rhodium Substances 0.000 claims abstract description 42
- 238000011068 loading method Methods 0.000 claims abstract description 25
- 239000002808 molecular sieve Substances 0.000 claims abstract description 22
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 16
- 150000001553 barium compounds Chemical class 0.000 claims abstract description 14
- 150000002697 manganese compounds Chemical class 0.000 claims abstract description 14
- 150000001785 cerium compounds Chemical class 0.000 claims abstract description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 7
- 239000010457 zeolite Substances 0.000 claims abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 3
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 116
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 76
- 229910052593 corundum Inorganic materials 0.000 claims description 68
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 68
- 238000001035 drying Methods 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 30
- 239000002131 composite material Substances 0.000 claims description 28
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 11
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 9
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 9
- 229940071125 manganese acetate Drugs 0.000 claims description 9
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 9
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 9
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 150000003058 platinum compounds Chemical class 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- VBEGUCKCABFDDF-UHFFFAOYSA-N hydroxylamine platinum Chemical compound [Pt].NO VBEGUCKCABFDDF-UHFFFAOYSA-N 0.000 claims description 7
- 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 claims description 7
- 239000007789 gas Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 4
- 229910001626 barium chloride Inorganic materials 0.000 claims description 4
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 4
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 4
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 4
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003284 rhodium compounds Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 7
- 229910021529 ammonia Inorganic materials 0.000 abstract description 3
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- 238000002156 mixing Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 7
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229940126142 compound 16 Drugs 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 229910002927 BaMnO3 Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910016978 MnOx Inorganic materials 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Inorganic materials [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000009323 psychological health Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract
The invention discloses a platinum-rhodium/barium-based catalytic material, a lean-burn nitrogen oxide catalyst and a preparation method thereof, wherein the platinum-rhodium/barium-based catalytic material comprises 0.1-1.1 wt% of platinum load, 0.01-0.12 wt% of rhodium load, 1-16 wt% of manganese compound, 1-10 wt% of cerium compound, 1-20 wt% of barium compound and the balance of aluminum oxide; the catalyst comprises a platinum-rhodium/barium-based catalytic material positioned in a front zone and an ASC catalytic material positioned in a rear zone, wherein in the ASC catalytic material, the platinum loading amount is 0.1-1.1 wt%, the metal oxide is 0.01-20%, and the balance is a zeolite molecular sieve. The catalyst can be used for reducing the emission of nitrogen oxides, remarkably improving the selectivity of nitrogen, efficiently inhibiting the generation of ammonia gas, resisting the water-thermal oxidation environment and being suitable for light diesel engines and lean-burn gasoline engines by coupling a platinum-rhodium/barium-based catalytic material with efficient nitrogen oxide removal performance and an ASC catalytic material with an ammonia oxidation function.
Description
Technical Field
The invention relates to a platinum-rhodium/barium-based catalytic material, a lean-burn nitrogen oxide catalyst and a preparation method thereof, in particular to a platinum-rhodium/barium-based catalytic material, a lean-burn nitrogen oxide NSR + ASC catalyst and a preparation method thereof, belonging to the technical field of catalytic purification of engine tail gas.
Background
With the rapid development of the automotive industry, environmental problems caused by the emission of automobile exhaust gases are particularly serious, among which Nitrogen Oxides (NO)x) Ammonia (NH)3) The discharge of nitrogen-containing gaseous pollutants brings great threats to the life quality, physical and psychological health of human beings.
The automobile exhaust purifying catalyst is the most effective technological means for controlling automobile exhaust. Due to fuel economy measures, engines employ lean burn technologyAnd (4) performing the operation. Conventional three-way catalysts are affected by air-fuel ratio to purify NOxPoor results, hence NO under lean conditionsxDecontamination has become one of the challenging issues in the environmental field.
Nitrogen oxide storage-reduction (NSR) technology with NOxHigh purification efficiency, wide temperature window, small space occupancy rate and the like, and is particularly suitable for light diesel engines and lean-burn gasoline engines. Pt/BaO/Al2O3Type NSR catalysts have been commercialized in lean burn gasoline engines without sulfur fuel, but the reduction in sulfur content in the fuel also results in a byproduct NH3And (4) discharge problems.
To meet national VI emissions regulations, catalytic converters must store NO during the lean burn phasexNO to be stored during rich burn phasexConversion to N2Reduction of by-product NH3And (4) generating. However, since NSR alone is not preferable, a technique that combines the NSR function and the catalytic ammoxidation activity is required.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide a platinum-rhodium/barium-based catalytic material, a lean-burn nitrogen oxide catalyst and a preparation method thereof, and the invention can overcome the defects of the prior Pt/BaO/Al catalyst2O3Type NSR catalytic material NH3Secondary pollutant generation, N2The catalyst has the advantages of low selectivity and poor hydrothermal stability, and has remarkable technical advantages in meeting the requirements of high activity, high selectivity and high stability of the automobile exhaust aftertreatment catalyst in the future.
The technical scheme of the invention is as follows:
a platinum-rhodium/barium-based catalytic material comprises 0.1-1.1 wt% of platinum, 0.01-0.12 wt% of rhodium, 1-16 wt% of manganese compound, 1-10 wt% of cerium compound, 1-20 wt% of barium compound and the balance of aluminum oxide; wherein the loading of each component is measured by the mass fraction of the component in the catalyst.
Preferably, the manganese compound is one or more of manganese nitrate, manganese acetate, manganese chloride and manganese oxide; the barium compound is one or more of barium nitrate, barium acetate, barium chloride and barium hydroxide; the cerium compound is one or more of cerium nitrate, cerium acetate, cerium sulfate and cerium oxide.
A lean burn nitrogen oxide catalyst comprising a platinum-rhodium/barium based catalytic material located in a front zone and an ASC catalytic material located in a rear zone; in the ASC catalytic material, the platinum loading is 0.1-1.1 wt%, the metal oxide is 0.01-20%, and the balance is zeolite molecular sieve; wherein the loading of each component is measured by the mass fraction of the component in the catalyst.
Preferably, the platinum-rhodium/barium-based catalytic material is x% of the mass of the lean-burn nitrogen oxide catalyst, wherein 60< x <100, and the balance is ASC catalytic material.
The invention also provides a platinum-rhodium/barium-based catalytic material and a preparation method of the lean-burn nitrogen oxide catalyst containing the platinum-rhodium/barium-based catalytic material, and the preparation method comprises the following steps:
(1) adding alumina into manganese compound solution, stirring, drying and roasting to obtain MnO2/Al2O3Composite material, further MnO2/Al2O3Adding the composite material into the barium compound solution, stirring, drying and roasting to obtain BaO/MnO2/Al2O3A composite material;
(2) taking a platinum compound in the solution as a precursor and reacting with BaO/MnO in the step (1)2/Al2O3Loading the composite material in a dipping mode, standing at room temperature, drying and roasting to prepare Pt/BaO/MnO2/Al2O3A catalytic material;
(3) loading rhodium compound in solution as precursor and cerium compound through soaking, standing at room temperature, drying and roasting to obtain Rh/CeO2A catalytic material;
(4) the Pt/BaO/MnO in the step (2)2/Al2O3Catalytic material and Rh/CeO in (3)2The catalytic material is physically mixed and roasted to prepare the platinum-rhodium/barium-based catalytic material.
(5) Loading the solution with inorganic metal salt as precursor and zeolite molecular sieve through impregnation or ion exchange, drying and roasting to obtain the metal modified zeolite molecular sieve material;
(6) and (3) taking a platinum compound in the solution as a precursor, loading the platinum compound and the metal modified zeolite molecular sieve material in the step (5) in a dipping or ion exchange mode, drying and roasting to obtain the ASC catalytic material.
Preferably, the platinum compound is one or more of platinum hydroxylamine, platinum tetraammine acetate, bis (ethanolamine) hexahydroxyplatinate, platinum nitrate and platinum tetraammine nitrate.
Preferably, the rhodium compound is one or more of rhodium nitrate and potassium chlororhodate.
Preferably, the manganese compound is one or more of manganese nitrate, manganese acetate, manganese chloride and manganese oxide.
Preferably, the barium compound is one or more of barium nitrate, barium acetate, barium chloride and barium hydroxide
Preferably, the cerium compound is one or more of cerium nitrate, cerium acetate, cerium sulfate and cerium oxide.
Preferably, the metal inorganic salt is one or more of inorganic salts of Ce, Mn, Co, Fe and Pr.
Preferably, the zeolite molecular sieve is one or more of USY series molecular sieve, Beta series molecular sieve, SSZ-13 series molecular sieve and ZSM-5 series molecular sieve.
Preferably, the standing time is 6-24 hours, the drying temperature is 100-150 ℃, the drying time is 2-24 hours, the roasting temperature is 400-850 ℃, and the roasting time is 1-6 hours.
The mechanism and the beneficial effects of the invention are as follows:
the NSR catalyst included in the present invention stores NO during lean burn phasexNO to be stored during rich burn phasexReduction to N2With a portion of NH3And the like. The cerium oxide in the platinum-rhodium/barium-based catalytic material can effectively stabilize active species, promote water gas conversion reaction, improve the reducibility of the catalyst, and improve the low-temperature NOx conversion efficiency and N of the catalyst2And (4) selectivity. The platinum-containing compound of the present inventionA lean-burn nitrogen oxide catalyst of rhodium/barium based catalytic material organically coupling the NSR function and the catalytic ammonia oxidation activity, the platinum-rhodium/barium based catalytic material being located at the inlet end of the reactor, Pt/Fe2O3the/USY ASC catalytic material is positioned at the gas outlet end, in the lean-burn stage, and unreacted O of the upstream platinum-rhodium/barium-based catalytic material2Adsorbed and dissociated into O by ASC catalytic materialadsThe required oxygen source is provided for the catalytic oxidation of the ASC catalytic material, and NH leaked from the upstream platinum-rhodium/barium-based catalytic material in the rich combustion stage3With previously adsorbed dissociated O on ASC catalytic materialadsInteraction of NH with3Rapid conversion to N2. The invention has higher low-temperature NOxRemoval performance, effective inhibition of NH3By-product formation, significantly increased N2The catalyst has the advantages of selectivity, high resistance to high-temperature hydrothermal oxidation environment, high hydrothermal stability, simple preparation method, easily obtained raw materials and suitability for industrial production, and is particularly suitable for light diesel engines and lean-burn gasoline engines.
Drawings
FIG. 1 is a schematic view of a zoned combination of a nitrogen oxide catalyst of the present invention, wherein: 1-an air inlet end; 2-platinum-rhodium/barium-based catalytic materials; 3-ASC catalytic material; 4-air outlet end.
Figure 2 is the XRD spectrum of the catalyst sample of example 1.
FIG. 3 is a graph of HAADF-STEM and EDS spectra of catalyst samples of example 1.
FIG. 4 is a graph of NO for comparative example and example 1 fresh and aged catalyst samplesxConversion is plotted.
FIG. 5 shows comparative example and example 1 fresh and aged catalyst samples N2And (4) selective contrast graph.
FIG. 6 shows NO of fresh catalyst samples of examples 1, 2, 3 and 4xConversion is plotted.
FIG. 7 shows NH of fresh catalyst samples of examples 1, 2, 3 and 43And (4) selective contrast graph.
FIG. 8 shows fresh catalyst samples N of examples 1, 2, 3 and 42Selective pair ofAnd (5) comparing the graph.
FIG. 9 shows the aged catalyst samples NO of examples 1, 2, 3 and 4xConversion is plotted.
FIG. 10 shows NH of aged catalyst samples of examples 1, 2, 3 and 43And (4) selective contrast graph.
FIG. 11 shows aged catalyst samples N of examples 1, 2, 3 and 42And (4) selective contrast graph.
Detailed Description
The present invention will be further described with reference to specific embodiments.
The present invention is further illustrated by the following comparative examples and examples, but the present invention is not limited thereto, and the same or similar techniques as those of the present invention are not beyond the scope of the present invention.
Comparative example: Rh-Pt/BaO/MnO2/Al2O3Catalytic material
The catalytic material comprises: platinum loading of 0.9 wt%, rhodium loading of 0.1 wt%, manganese compound of 8 wt%, barium compound of 16 wt%, and the balance of alumina; wherein the content of each component is measured by the mass fraction of the component in the catalyst.
The preparation method comprises the following steps:
weighing manganese dioxide and aluminum oxide containing 8 wt% of manganese acetate, adding into deionized water, stirring for 7h, drying in a constant temperature drying oven at 120 ℃ to constant weight, and roasting in a muffle furnace at 550 ℃ for 3h to obtain MnO2/Al2O3Composite material, barium oxide and MnO containing barium acetate to 16 wt%2/Al2O3Adding the composite material into deionized water, stirring, drying at constant temperature of 120 ℃ to constant weight, roasting at 550 ℃ in a muffle furnace for 3h, and finally performing heat treatment at 850 ℃ for 4h to obtain BaO/MnO2/Al2O3A composite material; mixing BaO/MnO2/Al2O3Adding the composite material liquid into deionized water to prepare 0.1-3mol/L hydroxylamine platinum solution, stirring for 2h, standing at room temperature for 12h, drying at constant temperature of 120 ℃ to constant weight, and roasting in a muffle furnace at 590 ℃ for 2h to obtain the composite materialPt/BaO/MnO2/Al2O3A catalytic material. Adding alumina into 0.1-1mol/L rhodium nitrate solution, stirring for 2h, standing at room temperature for 12h, drying at constant temperature of 120 ℃ to constant weight, and roasting at 590 ℃ in a muffle furnace for 2h to obtain Rh/Al2O3A catalytic material. Mixing Pt/BaO/MnO2/Al2O3And Rh/Al2O3Fully grinding after physical mixing to obtain fresh Rh-Pt/BaO/MnO2/Al2O3A catalytic material.
Roasting the fresh sample in a hydrothermal oxidation atmosphere at 750 ℃ for 10h to obtain aged Rh-Pt/BaO/MnO2/Al2O3A catalytic material. Hydrothermal oxidizing atmosphere: 10% H2O+10％O2+80％N2。
Rh-Pt/BaO/MnO2/Al2O3And the catalytic material is filled in a miniature fixed bed of the multifunctional catalyst evaluation device for performance evaluation. The reaction space velocity is 120000 ml.h-1·g-1。
Example 1: Rh/CeO2-Pt/BaO/MnO2/Al2O3Catalytic material
The catalytic material comprises: platinum loading of 0.9 wt%, rhodium loading of 0.1 wt%, manganese compound of 8 wt%, cerium compound of 5 wt%, barium compound of 16 wt%, and the balance of alumina; wherein the content of each component is measured by the mass fraction of the component in the catalyst.
The preparation method comprises the following steps:
weighing manganese dioxide and aluminum oxide containing 8 wt% of manganese acetate, adding into deionized water, stirring for 7h, drying in a constant temperature drying oven at 120 ℃ to constant weight, and roasting in a muffle furnace at 550 ℃ for 3h to obtain MnO2/Al2O3Composite material, barium oxide and MnO containing barium acetate to 16 wt%2/Al2O3Adding the composite material into deionized water, stirring, drying at constant temperature of 120 ℃ to constant weight, roasting at 550 ℃ in a muffle furnace for 3h, and finally performing heat treatment at 850 ℃ for 4h to obtain BaO/MnO2/Al2O3A composite material; mixing BaO/MnO2/Al2O3CompoundingAdding the material liquid into deionized water to prepare 0.1-3mol/L hydroxylamine platinum solution, stirring for 2h, standing at room temperature for 12h, drying at constant temperature of 120 ℃ to constant weight, and then roasting in a muffle furnace at 590 ℃ for 2h to obtain Pt/BaO/MnO2/Al2O3A catalytic material. Adding 5 wt% of cerium oxide metered by oxide into 0.1-1mol/L rhodium nitrate solution, stirring for 2h, standing at room temperature for 12h, drying at constant temperature of 120 ℃ to constant weight, and then roasting at 590 ℃ in a muffle furnace for 2h to obtain Rh/CeO2A catalytic material. Mixing Pt/BaO/MnO2/Al2O3And Rh/CeO2Fully grinding after physical mixing to obtain fresh Rh/CeO2-Pt/BaO/MnO2/Al2O3A catalytic material.
Roasting the fresh sample in a hydrothermal oxidation atmosphere at 750 ℃ for 10 hours to obtain aged Rh/CeO2-Pt/BaO/MnO2/Al2O3A catalytic material. Hydrothermal oxidizing atmosphere: 10% H2O+10％O2+80％N2。
Rh/CeO2-Pt/BaO/MnO2/Al2O3And the catalytic material is filled in a miniature fixed bed of the multifunctional catalyst evaluation device for performance evaluation. The reaction space velocity is 120000 ml.h-1·g-1。
Example 2: Rh/CeO2-Pt/BaO/MnO2/Al2O3Catalytic material and catalyst
The catalytic material comprises: platinum loading is 0.9%, rhodium loading is 0.1 wt%, manganese compound 8 wt%, cerium compound 5 wt%, barium compound 16 wt%, and the balance of alumina; wherein the content of each component is measured by the mass fraction of the component in the catalyst.
The catalyst comprises: the catalytic material accounts for 95% of the mass, and the balance is ASC catalytic material.
The preparation method comprises the following steps:
weighing manganese dioxide and aluminum oxide containing 8 wt% of manganese acetate, adding into deionized water, stirring for 7h, drying in a constant temperature drying oven at 120 ℃ to constant weight, and roasting in a muffle furnace at 550 ℃ for 3h to obtain MnO2/Al2O3Composite material ofBarium oxide and MnO containing barium acetate up to 16 wt%2/Al2O3Adding the composite material into deionized water, stirring, drying at constant temperature of 120 ℃ to constant weight, roasting at 550 ℃ in a muffle furnace for 3h, and finally performing heat treatment at 850 ℃ for 4h to obtain BaO/MnO2/Al2O3A composite material; mixing BaO/MnO2/Al2O3Adding the composite material liquid into deionized water to prepare 0.1-3mol/L hydroxylamine platinum solution, stirring for 2h, standing at room temperature for 12h, drying at constant temperature of 120 ℃ to constant weight, and then roasting in a muffle furnace at 590 ℃ for 2h to obtain Pt/BaO/MnO2/Al2O3A catalytic material. Adding 5 wt% of cerium oxide metered by oxide into 0.1-1mol/L rhodium nitrate solution, stirring for 2h, standing at room temperature for 12h, drying at constant temperature of 120 ℃ to constant weight, and then roasting at 590 ℃ in a muffle furnace for 2h to obtain Rh/CeO2A catalytic material. Mixing Pt/BaO/MnO2/Al2O3And Rh/CeO2Fully grinding after physical mixing to obtain fresh Rh/CeO2-Pt/BaO/MnO2/Al2O3A catalytic material.
Adding a USY molecular sieve into a 0.1-3mol/L platinum nitrate solution prepared from deionized water, stirring for 2h, standing at room temperature for 12h, drying at constant temperature of 120 ℃ to constant weight, roasting in a muffle furnace at 300 ℃ for 2h to obtain a Pt/USY catalytic material, adding the Pt/USY catalytic material and ferric oxide containing ferric nitrate to reach 5 wt% into a proper amount of deionized water, stirring for 2h, drying at constant temperature of 120 ℃ to constant weight, and roasting in the muffle furnace at 600 ℃ for 4h to obtain Pt/Fe2O3A USY catalytic material.
Roasting the fresh sample in a hydrothermal oxidation atmosphere at 750 ℃ for 10 hours to obtain aged Rh/CeO2-Pt/BaMn/Al2O3And Pt/Fe2O3A USY catalytic material. Hydrothermal oxidizing atmosphere: 10% H2O+10％O2+80％N2。
Rh/CeO2-Pt/BaO/MnO2/Al2O3Catalytic material and Pt/Fe2O3The mass ratio of the/USY catalytic material is 19, and the catalyst is filled in a micro fixed bed of a multifunctional catalyst evaluation device for performance evaluation. Rh/CeO2-Pt/BaO/MnO2/Al2O3Catalytic material at the inlet end of the reactor, Pt/Fe2O3the/USY catalytic material is positioned at the air outlet end. The reaction space velocity is 120000 ml.h-1·g-1。
Example 3: Rh/CeO2-Pt/BaO/MnO2/Al2O3Catalytic material and catalyst
The catalytic material comprises: platinum loading is 0.9%, rhodium loading is 0.1 wt%, manganese compound 8 wt%, cerium compound 5 wt%, barium compound 16 wt%, and the balance of alumina; wherein the content of each component is measured by the mass fraction of the component in the catalyst.
The catalyst comprises: the catalytic material accounts for 90% of the mass, and the balance is ASC catalytic material.
The preparation method comprises the following steps:
weighing manganese dioxide and aluminum oxide containing 8 wt% of manganese acetate, adding into deionized water, stirring for 7h, drying in a constant temperature drying oven at 120 ℃ to constant weight, and roasting in a muffle furnace at 550 ℃ for 3h to obtain MnO2/Al2O3Composite material, barium oxide and MnO containing barium acetate to 16 wt%2/Al2O3Adding the composite material into deionized water, stirring, drying at constant temperature of 120 ℃ to constant weight, roasting at 550 ℃ in a muffle furnace for 3h, and finally performing heat treatment at 850 ℃ for 4h to obtain BaO/MnO2/Al2O3A composite material; mixing BaO/MnO2/Al2O3Adding the composite material liquid into deionized water to prepare 0.1-3mol/L hydroxylamine platinum solution, stirring for 2h, standing at room temperature for 12h, drying at constant temperature of 120 ℃ to constant weight, and then roasting in a muffle furnace at 590 ℃ for 2h to obtain Pt/BaO/MnO2/Al2O3A catalytic material. Adding 5 wt% of cerium oxide metered by oxide into 0.1-1mol/L rhodium nitrate solution, stirring for 2h, standing at room temperature for 12h, drying at constant temperature of 120 ℃ to constant weight, and then roasting at 590 ℃ in a muffle furnace for 2h to obtain Rh/CeO2A catalytic material. Mixing Pt/BaO/MnO2/Al2O3And Rh/CeO2Fully grinding after physical mixing to obtain fresh Rh/CeO2-Pt/BaO/MnO2/Al2O3A catalytic material.
Adding a USY molecular sieve into a 0.1-3mol/L platinum nitrate solution prepared from deionized water, stirring for 2h, standing at room temperature for 12h, drying at constant temperature of 120 ℃ to constant weight, roasting in a muffle furnace at 300 ℃ for 2h to obtain a Pt/USY catalytic material, adding the Pt/USY catalytic material and ferric oxide containing ferric nitrate to reach 5 wt% into a proper amount of deionized water, stirring for 2h, drying at constant temperature of 120 ℃ to constant weight, and roasting in the muffle furnace at 600 ℃ for 4h to obtain Pt/Fe2O3A USY catalytic material.
Roasting the fresh sample in a hydrothermal oxidation atmosphere at 750 ℃ for 10 hours to obtain aged Rh/CeO2-Pt/BaMn/Al2O3And Pt/Fe2O3A USY catalytic material. Hydrothermal oxidizing atmosphere: 10% H2O+10％O2+80％N2。
Rh/CeO2-Pt/BaO/MnO2/Al2O3Catalytic material and Pt/Fe2O3The mass ratio of the/USY catalytic material is 9, and the catalyst is filled in a miniature fixed bed of a multifunctional catalyst evaluation device for performance evaluation. Rh/CeO2-Pt/BaO/MnO2/Al2O3Catalytic material at the inlet end of the reactor, Pt/Fe2O3the/USY catalytic material is positioned at the air outlet end. The reaction space velocity is 120000 ml.h-1·g-1。
Example 4: Rh/CeO2-Pt/BaO/MnO2/Al2O3Catalytic material and catalyst
The catalytic material comprises: platinum loading is 0.9%, rhodium loading is 0.1 wt%, manganese compound 8 wt%, cerium compound 5 wt%, barium compound 16 wt%, and the balance of alumina; wherein the content of each component is measured by the mass fraction of the component in the catalyst.
The catalyst comprises: the catalytic material accounts for 80% of the mass, and the balance is ASC catalytic material.
The preparation method comprises the following steps:
weighing manganese dioxide and aluminum oxide containing 8 wt% of manganese acetate, adding into deionized water, stirring for 7h, drying in a 120 deg.C constant temperature drying oven to constant weight, and dryingRoasting at 550 ℃ in a muffle furnace for 3h to obtain MnO2/Al2O3Composite material, barium oxide and MnO containing barium acetate to 16 wt%2/Al2O3Adding the composite material into deionized water, stirring, drying at constant temperature of 120 ℃ to constant weight, roasting at 550 ℃ in a muffle furnace for 3h, and finally performing heat treatment at 850 ℃ for 4h to obtain BaO/MnO2/Al2O3A composite material; mixing BaO/MnO2/Al2O3Adding the composite material liquid into deionized water to prepare 0.1-3mol/L hydroxylamine platinum solution, stirring for 2h, standing at room temperature for 12h, drying at constant temperature of 120 ℃ to constant weight, and then roasting in a muffle furnace at 590 ℃ for 2h to obtain Pt/BaO/MnO2/Al2O3A catalytic material. Adding 5 wt% of cerium oxide metered by oxide into 0.1-1mol/L rhodium nitrate solution, stirring for 2h, standing at room temperature for 12h, drying at constant temperature of 120 ℃ to constant weight, and then roasting at 590 ℃ in a muffle furnace for 2h to obtain Rh/CeO2A catalytic material. Mixing Pt/BaO/MnO2/Al2O3And Rh/CeO2Fully grinding after physical mixing to obtain fresh Rh/CeO2-Pt/BaO/MnO2/Al2O3A catalytic material.
Adding a USY molecular sieve into a 0.1-3mol/L platinum nitrate solution prepared from deionized water, stirring for 2h, standing at room temperature for 12h, drying at constant temperature of 120 ℃ to constant weight, roasting in a muffle furnace at 300 ℃ for 2h to obtain a Pt/USY catalytic material, adding the Pt/USY catalytic material and ferric oxide containing ferric nitrate to reach 5 wt% into a proper amount of deionized water, stirring for 2h, drying at constant temperature of 120 ℃ to constant weight, and roasting in the muffle furnace at 600 ℃ for 4h to obtain Pt/Fe2O3A USY catalytic material.
Roasting the fresh sample in a hydrothermal oxidation atmosphere at 750 ℃ for 10 hours to obtain aged Rh/CeO2-Pt/BaMn/Al2O3And Pt/Fe2O3A USY catalytic material. Hydrothermal oxidizing atmosphere: 10% H2O+10％O2+80％N2。
Rh/CeO2-Pt/BaO/MnO2/Al2O3Catalytic material and Pt/Fe2O3The mass ratio of the USY catalytic material is 4, and the USY catalytic material is filled in a multifunctional catalystThe performance was evaluated in a mini-fixed bed of the chemical agent evaluation apparatus. Rh/CeO2-Pt/BaO/MnO2/Al2O3Catalytic material at the inlet end of the reactor, Pt/Fe2O3the/USY catalytic material is positioned at the air outlet end. The reaction space velocity is 120000 ml.h-1·g-1。
As can be seen from fig. 2 and 3:
in example 1, Mn species are mainly MnOx, BaMnO3In the form of Ba species predominantly as BaCO3And BaMnO3The form exists.
Examples 1-4 of the present invention have beneficial technical effects:
as can be seen from fig. 4 and 5:
example 1 comparison with comparative example, CeO2Is beneficial to improving the low-temperature NO of the catalystxConversion efficiency, N2Selectivity and hydrothermal stability.
As can be seen from fig. 6, 7 and 8:
examples 2, 3, and 4 fresh catalyst samples compared to comparative examples, the combination of the platinum-rhodium/barium-based catalytic material and the ASC catalytic material in zones improved the low temperature NO of the catalyst as a wholexConversion efficiency and N2Selective, effective inhibition of NH3And (4) generating.
As can be seen from fig. 9, 10 and 11:
examples 2, 3, 4 aged catalyst samples compared to comparative examples, also have improved catalyst integrity in the aged low temperature NOxConversion efficiency, increase of N2Selective, NH-suppression3Formation of N, especially at low temperatures2Rate of selectivity deterioration<20％，NH3The selectivity is reduced by about 60 percent, which shows that the catalytic material can resist a hydrothermal oxidation environment, has high thermal stability and application potential in an automobile exhaust aftertreatment catalyst.
Claims (11)
1. A platinum-rhodium/barium-based catalytic material, the catalytic material comprising:
platinum loading capacity of 0.1-1.1 wt%, rhodium loading capacity of 0.01-0.12 wt%, manganese compound 1-16 wt%, cerium compound 1-10 wt%, barium compound 1-20 wt%, and the balance of aluminum oxide; wherein the content of each component is measured by the mass fraction of the component in the catalyst.
2. The platinum-rhodium/barium-based catalytic material of claim 1, wherein:
the manganese compound is one or more of manganese nitrate, manganese acetate, manganese chloride and manganese oxide.
3. The platinum-rhodium/barium-based catalytic material of claim 1, wherein:
the barium compound is one or more of barium nitrate, barium acetate, barium chloride and barium hydroxide.
4. The platinum-rhodium/barium-based catalytic material of claim 1, wherein:
the cerium compound is one or more of cerium nitrate, cerium acetate, cerium sulfate and cerium oxide.
5. A lean-burn nitrogen oxide catalyst comprising the platinum-rhodium/barium-based catalytic material as claimed in any one of claims 1 to 4, characterized in that:
including a platinum-rhodium/barium-based catalytic material located in a front region of the lean-burn nitrogen oxide catalyst and an ASC catalytic material located in a rear region of the lean-burn nitrogen oxide catalyst; in the ASC catalytic material, the platinum loading is 0.1-1.1 wt%, the metal oxide is 0.01-20%, and the balance is zeolite molecular sieve; wherein the content of each component is measured by the mass fraction of the component in the catalyst.
6. The lean burn nitrogen oxide catalyst of claim 5, wherein:
the platinum-rhodium/barium-based catalytic material is x% of the mass of the lean-burn nitrogen oxide catalyst, wherein x is more than 60 and less than 100, and the balance is ASC catalytic material.
7. A process for the preparation of a platinum-rhodium/barium-based catalytic material according to any one of claims 1 to 4, characterized in that it comprises the following steps:
(1) adding alumina into manganese compound solution, stirring, drying and roasting to obtain MnO2/Al2O3Composite material, further MnO2/Al2O3Adding the composite material into the barium compound solution, stirring, drying and roasting to obtain BaO/MnO2/Al2O3A composite material;
(2) taking a platinum compound in the solution as a precursor and reacting with BaO/MnO in the step (1)2/Al2O3Loading the composite material in a dipping mode, standing at room temperature, drying and roasting to prepare Pt/BaO/MnO2/Al2O3A catalytic material;
(3) loading rhodium compound in solution as precursor and cerium compound through soaking, standing at room temperature, drying and roasting to obtain Rh/CeO2A catalytic material;
(4) the Pt/BaO/MnO in the step (2)2/Al2O3Catalytic material and Rh/CeO in (3)2The catalytic material is physically mixed and roasted to prepare the platinum-rhodium/barium-based catalytic material.
8. The process for the preparation of a platinum-rhodium/barium-based catalytic material according to claim 7, characterized in that:
the platinum compound is one or more of platinum hydroxylamine, platinum tetraammine acetate, di (ethanolamine) hexahydroxyplatinate, platinum nitrate and platinum tetraammine nitrate;
the rhodium compound is one or more of rhodium nitrate and potassium chlororhodate;
the manganese compound is one or more of manganese nitrate, manganese acetate, manganese chloride and manganese oxide;
the barium compound is one or more of barium nitrate, barium acetate, barium chloride and barium hydroxide;
the cerium compound is one or more of cerium nitrate, cerium acetate, cerium sulfate and cerium oxide.
9. A method for preparing a lean burn nitrogen oxide catalyst as claimed in claim 5 or 6, comprising the steps of:
(1) the platinum-rhodium/barium-based catalytic material prepared according to the preparation method of platinum-rhodium/barium-based catalytic material of claim 7 or 8;
(2) loading the solution with inorganic metal salt as precursor and zeolite molecular sieve through impregnation or ion exchange, drying and roasting to obtain the metal modified zeolite molecular sieve material;
(3) and (3) taking a platinum compound in the solution as a precursor, loading the platinum compound and the metal modified zeolite molecular sieve material in the step (2) in a dipping or ion exchange mode, drying and roasting to obtain the ASC catalytic material.
10. The method of making a lean burn nitrogen oxide catalyst as recited in claim 9, wherein:
the metal inorganic salt is one or more of inorganic salts in Ce, Mn, Co, Fe and Pr;
the zeolite molecular sieve is one or more of USY series molecular sieve, Beta series molecular sieve, SSZ-13 series molecular sieve and ZSM-5 series molecular sieve;
the standing time is 6-24 hours, the drying temperature is 100-150 ℃, the drying time is 2-24 hours, the roasting temperature is 400-850 ℃, and the roasting time is 1-6 hours.
11. The lean-burn nitrogen oxide catalyst according to claim 5 or 6, for use in exhaust gas after-treatment of a light-duty diesel engine or a lean-burn gasoline engine.
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