CN114984969A - Three-way catalyst and preparation method and application thereof - Google Patents
Three-way catalyst and preparation method and application thereof Download PDFInfo
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- CN114984969A CN114984969A CN202210823374.8A CN202210823374A CN114984969A CN 114984969 A CN114984969 A CN 114984969A CN 202210823374 A CN202210823374 A CN 202210823374A CN 114984969 A CN114984969 A CN 114984969A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 197
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000010949 copper Substances 0.000 claims abstract description 170
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 130
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 68
- 229910052802 copper Inorganic materials 0.000 claims abstract description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 238000007598 dipping method Methods 0.000 claims abstract description 9
- 238000011068 loading method Methods 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000000376 reactant Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 27
- 239000000446 fuel Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- 238000005470 impregnation Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 150000004677 hydrates Chemical class 0.000 claims description 11
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 4
- 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 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- PGJHGXFYDZHMAV-UHFFFAOYSA-K azanium;cerium(3+);disulfate Chemical compound [NH4+].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O PGJHGXFYDZHMAV-UHFFFAOYSA-K 0.000 claims description 2
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 claims description 2
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-O azanium;hydron;hydroxide Chemical compound [NH4+].O VHUUQVKOLVNVRT-UHFFFAOYSA-O 0.000 claims 2
- WTVAYLQYAWAHAX-UHFFFAOYSA-J cerium(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Ce+4] WTVAYLQYAWAHAX-UHFFFAOYSA-J 0.000 claims 2
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 abstract description 64
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 54
- 239000001301 oxygen Substances 0.000 abstract description 54
- 230000003197 catalytic effect Effects 0.000 abstract description 46
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 abstract description 12
- 239000011593 sulfur Substances 0.000 abstract description 12
- 238000003860 storage Methods 0.000 abstract description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 175
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 72
- 239000003344 environmental pollutant Substances 0.000 description 24
- 239000007789 gas Substances 0.000 description 24
- 231100000719 pollutant Toxicity 0.000 description 24
- 230000000694 effects Effects 0.000 description 15
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- 230000009467 reduction Effects 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
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- 239000003546 flue gas Substances 0.000 description 7
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- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
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- 230000009286 beneficial effect Effects 0.000 description 3
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- 238000006479 redox reaction Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
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- 230000002035 prolonged effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N Nitrogen oxide(NO) Natural products O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 1
- VMKYLARTXWTBPI-UHFFFAOYSA-N copper;dinitrate;hydrate Chemical compound O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O VMKYLARTXWTBPI-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- 238000002411 thermogravimetry Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- 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
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a three-way catalyst, a preparation method and application thereof, and belongs to the field of automobile exhaust treatment. The three-way catalyst comprises the following components: gamma-Al 2 O 3 A carrier; CeZrSnO 2 Auxiliary agent, CeZrSnO 2 The auxiliary agent enters the gamma-Al through a dipping mode 2 O 3 In a carrier to form CeZrSnO 2 /γ‑Al 2 O 3 A complex; and active metal copper, wherein the active metal copper enters the CeZrSnO through a dipping mode 2 /γ‑Al 2 O 3 In a complex. The three-way catalyst of the invention consists ofIn CeZrSnO 2 The presence of the auxiliary agent improves the sulfur resistance, thereby increasing the catalytic activity of the three-way catalyst and prolonging the service life of the three-way catalyst, and the auxiliary agent has excellent oxygen storage and release performance, thereby achieving the purpose of efficiently removing CO, NO and C in automobile exhaust with low cost and wider oxygen concentration operation space x H y 。
Description
Technical Field
The invention relates to the field of automobile exhaust treatment, in particular to a three-way catalyst and a preparation method and application thereof.
Background
At present, automobiles become the main means of transportation for people going out. However, the automobile brings convenience to people to go out, and the pollutants discharged by the automobile also have potential influence on the ambient air. According to statistics, the total emission amount of four pollutants of motor vehicles nationwide in one year is 1593.0 ten thousand tons. In particular carbon monoxide (CO), hydrocarbons (CH or C) x H y ) Nitrogen Oxide (NO) x ) And the emission amount of the Particulate Matter (PM) is 769.7 ten thousand tons, 190.2 ten thousand tons, 626.3 ten thousand tons and 6.8 ten thousand tons respectively. Especially, automobiles are the main contributors to the total amount of pollutants that emit carbon monoxide (CO), hydrocarbons (CH), and Nitrogen Oxides (NO) x ) And Particulate Matter (PM) exceeding 90% of the total vehicle emissions. The pollutants not only destroy the natural ecological environment, but also harm the health of people.
In practice, three-way catalysts can be used to remove pollutants such as CO, NO, C from automobile exhaust x H y And the like. However, although the current commercial three-way catalyst has high catalytic efficiency, it is very easy to generate sulfur poisoning and deactivation, and is not easy to regenerate and needs to be replaced frequently, resulting in increased use cost and reduced pollutant removal efficiency.
Disclosure of Invention
In order to solve at least one aspect of the above problems and disadvantages in the prior art, embodiments of the present invention provide a three-way catalyst, a method for preparing the same, and a method for removing CO, NO, and C in automobile exhaust using the three-way catalyst x H y The use of (1).
According to one aspect of the present invention, there is provided a three-way catalyst consisting of: gamma-Al 2 O 3 A carrier; CeZrSnO 2 Auxiliary agent, CeZrSnO 2 The auxiliary agent enters the gamma-Al through a dipping mode 2 O 3 In a carrier to form CeZrSnO 2 /γ-Al 2 O 3 A complex; and active metal copper, wherein the active metal copper enters the CeZrSnO through a dipping mode 2 /γ-Al 2 O 3 In a complex.
According to another aspect of the present invention, there is provided a method of preparing the three-way catalyst according to the above embodiment, comprising: providing gamma-Al 2 O 3 A carrier; providing a first mixed solution of a cerium source, a zirconium source, and a tin source; subjecting the gamma-Al to 2 O 3 Mixing a carrier and the first mixed solution to form a second mixed solution, adding an ammonia water solution into the second mixed solution for impregnation and loading to obtain a first reactant, and roasting the first reactant to obtain CeZrSnO 2 /γ-Al 2 O 3 A complex; CeZrSnO 2 /γ-Al 2 O 3 The composite and the solution of the copper source are mixed and carried out water bath impregnation loading to obtain a second reactant, and the second reactant is roasted to obtain a Cu/CeZrSnO composite 2 /γ- Al 2 O 3 The three-way catalyst of (1).
According to another aspect of the invention, the invention provides a three-way catalyst for removing CO, NO and C in automobile exhaust x H y The three-way catalyst is the three-way catalyst prepared by the preparation method of the embodiment, wherein the three-way catalyst is used for removing CO, NO and C in automobile exhaust at the space velocity of 30000/h-60000/h, the air-fuel ratio of 0.8-1.075 and the reaction temperature of 500-800 DEG C x H y 。
The three-way catalyst and the preparation method and application thereof according to the invention have at least one of the following advantages:
(1)the three-way catalyst of the invention is formed by CeZrSnO 2 The sulfur resistance of the three-way catalyst is improved due to the existence of the auxiliary agent (such as the action of Sn), and the service life of the catalyst is prolonged;
(2) the three-way catalyst of the invention is formed by CeZrSnO 2 The existence of the auxiliary agent (such as the function of Sn) has excellent functions of oxygen storage and oxygen release, the oxygen content can be effectively adjusted, and the air-fuel ratio operation space of the three-way catalyst is effectively widened;
(3) the three-way catalyst of the invention is formed by CeZrSnO 2 The presence of the auxiliary agent (such as the action of Sn) improves the catalytic activity of the active component;
(4) the three-way catalyst uses copper with relatively low cost as an active component, reduces the cost of the three-way catalyst, and is beneficial to realizing industrial large-scale application;
(5) the three-way catalyst of the invention uses gamma-Al 2 O 3 A carrier having a high specific surface area and a high adsorption capacity, facilitating high dispersion loading of an active component on the carrier;
(6) the preparation method has simple preparation process, and can efficiently remove CO, NO and C in the automobile exhaust with low cost x H y The object of (a);
(7) the three-way catalyst has simple application process and can efficiently realize CO, NO and C in the automobile exhaust x H y And (4) removing.
Drawings
These and/or other aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the preferred embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 illustrates a method of making a three-way catalyst according to an embodiment of the invention;
FIGS. 2(a), (b), and (c) are the three-way catalyst Cu/CeZrSnO with different copper loading in the examples of the present invention 2 /γ-Al 2 O 3 The efficiency curves of the catalytic conversion of CO (a), NO (b), CH (c) are shown;
FIG. 3 shows Cu/CeZrSn with different Cu loading amounts in the examples of the present inventionO 2 /γ-Al 2 O 3 XRD spectrum of the catalyst;
FIGS. 4(a), (b), and (c) are schematic diagrams illustrating the effect of different Sn doping amounts on the catalyst activity in the embodiment of the present invention, respectively;
FIGS. 5(a), (b), and (c) are Cu/CeZrSnO at different baking temperatures in examples of the present invention 2 /γ-Al 2 O 3 The efficiency of catalytic conversion of CO, NO and CH is shown schematically;
in FIG. 6, (a), (b), (c) are 0.05% SO 2 Cu/CeZrO under the conditions 2 /γ-Al 2 O 3 And Cu/CeZrSnO of the inventive examples 2 /γ-Al 2 O 3 A schematic diagram of the catalytic conversion efficiency of CO, NO and CH by the catalyst;
FIG. 7 shows Cu/CeZrO 2 /γ-Al 2 O 3 And Cu/CeZrSnO of the inventive examples 2 /γ-Al 2 O 3 An XRD pattern of (a);
FIGS. 8(a), (b), (c), (d) are XPS spectra of (a) Ce 3d, (b) Cu2p, (c) O1s, (d) Zr 3d, Sn 3d, respectively, in the three-way catalyst of the example of the present invention;
FIG. 9 shows Cu/CeZrO 2 /γ-Al 2 O 3 And Cu/CeZrSnO of the inventive examples 2 /γ-Al 2 O 3 H of (A) to (B) 2 -a TPR map;
FIG. 10 shows Cu/CeZrO 2 /γ-Al 2 O 3 And Cu/CeZrSnO of the inventive examples 2 /γ-Al 2 O 3 O of (A) to (B) 2 -a TPD map;
FIG. 11 shows SO 2 TG profile of the treated three-way catalyst of the example of the invention;
FIG. 12(a), (b), and (c) are the Cu/CeZrSnO of the present invention at different airspeeds 2 /γ-Al 2 O 3 The efficiency of catalytic conversion of CO, NO and CH is shown schematically;
FIGS. 13(a) and (b) are Cu/CeZrO respectively 2 /γ-Al 2 O 3 (a) Cu/CeZrSnO of the embodiment of the invention 2 /γ-Al 2 O 3 (b) An air-fuel ratio window characteristic curve diagram of (1);
FIGS. 14(a), (b), and (c) are Cu/CeZrSnO samples of examples of the present invention at different reaction temperatures 2 /γ- Al 2 O 3 The efficiency of catalytic conversion of CO, NO, CH is shown schematically.
Detailed Description
The technical scheme of the invention is further specifically described by the following embodiments and the accompanying drawings. In the specification, the same or similar reference numerals denote the same or similar components. The following description of the embodiments of the present invention with reference to the accompanying drawings is intended to explain the general inventive concept of the present invention and should not be construed as limiting the invention.
In an embodiment of the present invention, a three-way catalyst is provided. The three-way catalyst comprises the following components: gamma-Al 2 O 3 Carrier, CeZrSnO 2 Auxiliary agent and active metal copper. The CeZrSnO 2 The auxiliary agent enters the gamma-Al through a dipping mode 2 O 3 In a carrier to form CeZrSnO 2 /γ-Al 2 O 3 And (c) a complex. The active metal copper enters the CeZrSnO in a dipping mode 2 /γ-Al 2 O 3 In a complex. That is, the three-way catalyst of the present invention is constituted of Cu/CeZrSnO 2 /γ-Al 2 O 3 。
The three-way catalyst of the examples of the present invention was prepared as gamma-Al 2 O 3 As a carrier by reacting with gamma-Al 2 O 3 The carrier is subjected to a two-step impregnation method to prepare CeZrSnO 2 Auxiliary agent and active metal copper loaded to gamma-Al 2 O 3 On a carrier, thereby obtaining Cu/CeZrSnO 2 /γ-Al 2 O 3 A three-way catalyst. The three-way catalyst has excellent sulfur resistance and oxygen storage performance, so that the catalytic activity is increased and the service life is prolonged.
Specifically, CeZrSnO in the three-way catalyst of the invention 2 The auxiliary (specifically, modification of Sn) can improve the sulfur resistance of the three-way catalyst. The modification of Sn can reduce SO adsorbed on the surface of active component (Cu) 2 SO that SO is adsorbed 2 Is not easy to be adsorbed around Cu to inhibit sulfuric acid on active componentsThe formation of salts. The formation of sulfates (e.g. ammonium sulfate and metal sulfates) is SO 2 The main cause of catalyst deactivation in the presence of water. The doping of Sn inhibits the formation of sulfate on the surface of the catalyst, particularly on the active component Cu, SO that the sulfur resistance of the three-way catalyst is improved, and the sulfur resistance of the three-way catalyst is improved, SO that the catalyst is subjected to SO treatment 2 Has better catalytic activity in the presence of the catalyst.
CeZrSnO in the three-way catalyst 2 The auxiliary agent (in particular, modification of Sn) allows the three-way catalyst to be applied under wider oxygen concentration operation space, such as removing CO, NO and C in automobile exhaust x H y . Tin (Sn) has two valence states of +2 and +4, so that the doping of Sn belongs to the doping of valence-variable ions, and the generation of extrinsic oxygen vacancies is caused. While extrinsic oxygen vacancies lead to the production of trivalent Ce, which satisfies (1-a) CeO 2 + aSnO→Ce 1-a Sn a O 2-a + Vo, where Vo is an oxygen vacancy. So that doping of Sn increases Ce on the surface of the catalyst 3+ Content and generate rich oxygen vacancy. The abundant oxygen vacancies are conducive to the adsorption of reactant gases, creating conditions for the oxidation reaction. Therefore, the activity of the catalyst for oxidizing CO and CH can be greatly improved by increasing the oxygen vacancy of the catalyst. That is, CeZrSnO 2 The auxiliary agent has the functions of oxygen storage and oxygen release. The three-way catalyst can exert better three-way catalytic performance only under the condition that the theoretical air-fuel ratio is in a smaller range, so the actual air-fuel ratio has a crucial influence on the efficiency of the three-way catalyst, and the catalytic assistant has the functions of oxygen storage and oxygen release, can effectively adjust the oxygen content, and further effectively broadens the air-fuel ratio operation space of the three-way catalyst.
CeZrSnO in the three-way catalyst 2 The promoter (in particular, modification of Sn) can also improve the catalytic efficiency of the metal active component. This is because both Cu and Ce have a smaller electronegativity than Sn, so that Cu undergoes a redox reaction 1+ +Sn 4+ →Cu 2+ +Sn 2+ To the right, thereby increasing Cu 2+ The content of (a). Cu 2+ Is an active component with main catalytic effect, the higher the relative content of the active component is, the more beneficial to improving the oxidation reduction capability of the catalyst, and further improving the metal activityCatalytic efficiency of the sexual component.
The three-way catalyst adopts gamma-Al 2 O 3 The carrier has high specific surface area and high adsorption capacity, has good compatibility with the active component, is easy to combine with the active component, and is favorable for high-degree dispersed loading of the active component on the carrier; and, gamma-Al 2 O 3 The carrier has a high porosity structure, and a plurality of unit cell gaps and defects exist in the crystal, so that the carrier has high activity.
In addition, the three-way catalyst of the embodiment of the invention adopts copper as an active ingredient, and compared with the common noble metal, the cost of the Cu is low, so that the cost of the three-way catalyst is effectively reduced.
In one example, Sn is in CeZrSnO 2 The mole ratio of the auxiliary agent is 5-30%, preferably 8-15%, and more preferably 10%. When the doping amount of Sn is 10%, CeZrO 2 The solid solution can generate lattice defects, broaden oxygen transfer channels and enhance oxygen transfer capacity. With increasing Sn doping, CeZrO 2 The cubic distortion degree of the solid solution is increased, the stability of the formed cubic phase is reduced, the oxygen transfer is not favored kinetically, meanwhile, the Ce content is reduced, the oxygen storage capacity of the auxiliary agent is insufficient, enough oxygen can not be provided for the oxidation-reduction reaction, and the catalytic performance is reduced along with the reduction.
In one example, in CeZrSnO 2 In the auxiliary agent, the molar ratio of Ce to Zr is (2-5): 1, preferably 3: 1.
by selecting Sn in CeZrSnO 2 The molar ratio of the auxiliary agent to the Ce/Zr can provide a three-way catalyst having an excellent effect of removing exhaust gas. For example, in CeZrSnO 2 In the auxiliary agent, the molar ratio n (Ce) to n (Zr) to n (Sn) of cerium, zirconium and tin is selected to be 0.675 to 0.225 to 0.1; the three-way catalyst comprising the auxiliary agent has good effect of removing CO, NO and CH in automobile exhaust, and the removal rate can reach 92%, 95% and 100% respectively.
In one example, the mass fraction of copper in the three-way catalyst is 1 wt% to 10 wt%, preferably 5 wt% to 10 wt%, more preferably 7 wt% to 9 wt%. Copper is the main active component in the three-way catalyst. As the loading of copper increases, the catalytic activity will increase continuously; however, when the loading amount of copper is too large, too much copper species may be accumulated on the surface of the carrier, and the agglomeration may cause a decrease in the specific surface area of the catalyst and unnecessary waste of resources.
In one example, γ -Al 2 O 3 Carrier and CeZrSnO 2 The mass ratio of the auxiliary agent is 25 (2-8), preferably 25 (4-6). By selecting the mass ratio of the carrier to the auxiliary agent, the removal efficiency of the three-way catalyst on the automobile exhaust can be improved under the condition of considering the cost.
In another embodiment of the present invention, a method of making a three-way catalyst is provided. As shown in fig. 1, the preparation method comprises:
providing gamma-Al 2 O 3 A carrier;
providing a first mixed solution of a cerium source, a zirconium source, and a tin source;
subjecting the gamma-Al to 2 O 3 Mixing a carrier and the first mixed solution to form a second mixed solution, adding an alkaline solution (such as an ammonia water solution) into the second mixed solution for impregnation and loading to obtain a first reactant, roasting the first reactant to remove moisture and other substances in the first reactant to obtain CeZrSnO 2 /γ-Al 2 O 3 A complex;
CeZrSnO 2 /γ-Al 2 O 3 Mixing the composite and a solution of a copper source, carrying out water bath impregnation loading to obtain a second reactant, roasting the second reactant to decompose the impregnated copper source, and obtaining the Cu/CeZrSnO composite 2 /γ- Al 2 O 3 The three-way catalyst of (1).
The preparation method of the three-way catalyst provided by the embodiment of the invention adopts a two-step impregnation method to prepare Cu/CeZrSnO 2 /γ-Al 2 O 3 The preparation method of the three-way catalyst has the advantages of simple process flow, environmental protection and obvious cost advantage.
In one example, γ -Al is provided 2 O 3 During the support, the pseudoboehmite powder (e.g., in a muffle furnace) is calcined at 700 ℃ to 900 ℃ (e.g., 800 ℃) for 3 to 5 hours (e.g., 4 hours). This is oneThe process can remove water from the alumina to obtain activated alumina, i.e. gamma-Al 2 O 3 . For example, the pseudoboehmite powder is calcined in a muffle furnace at a temperature ramp rate of 5 ℃/min up to 800 ℃ for 4 hours.
In one example, the cerium source includes at least one of cerium nitrate and a hydrate thereof, cerium chloride and a hydrate thereof, ammonium cerium nitrate and a hydrate thereof, ammonium cerium sulfate and a hydrate thereof.
In one example, the zirconium source comprises at least one of zirconium chloride and hydrates thereof, zirconyl nitrate and hydrates thereof, and zirconium acetate and hydrates thereof.
In one example, the tin source includes at least one of tin nitrate and hydrates thereof, tin tetrachloride and hydrates thereof, and tin acetate and hydrates thereof.
In one example, a cerium source, a zirconium source, and a tin source may be dissolved in ultrapure water to form a first mixed solution.
In obtaining the first reactant, an aqueous ammonia solution of 20 to 30mol/L (e.g., 25mol/L) is added to the second mixed solution under stirring (e.g., magnetic stirring), and a precipitate (i.e., the first reactant) is obtained when the pH reaches 9 to 12 (e.g., pH reaches 10).
In the calcination of the first reactant, the first reactant is dried at 105 ℃ and 120 ℃ (e.g., 110 ℃) for 10-15 hours (e.g., 11-13 hours, and further e.g., 12 hours), and then calcined at 600 ℃ and 800 ℃ (e.g., 700 ℃) for 2-5 hours (e.g., 3-4 hours) (e.g., in a muffle furnace). This removes nitrogen-containing species and moisture from the first reactant.
Alternatively, the first reactant may be ground into a powder after it is dried, and then calcined for 4 hours in a muffle furnace at a ramp rate of 5 ℃/min to 700 ℃.
In one example, the copper source includes at least one of copper nitrate and hydrates thereof, copper chloride and hydrates thereof.
Alternatively, a copper source (e.g., copper nitrate hydrate) may be dissolved in ultrapure water with stirring to form a solution of the copper source.
In the process of obtaining the second reactant, CeZrSnO 2 /γ-Al 2 O 3 The complex is mixed with a solution of the copper source and then subjected to a water bath immersion load at a temperature of 50-80 deg.C (e.g., 60-70 deg.C) for a period of 0.5-3 hours (e.g., 1-2 hours). This makes it possible to load the metal active component onto the carrier.
In the process of calcining the second reactant, the second reactant is dried at 105-120 deg.C (e.g., 110 deg.C) for 10-15 hours (e.g., 11-13 hours), and then calcined at 600-800 deg.C (e.g., 700 deg.C) for 1-3 hours (e.g., 1.5-2.5 hours). This may cause decomposition of the copper salt species.
Alternatively, the second reactant may be ground into a powder after it is dried, and then calcined for 2 hours in a muffle furnace at a ramp rate of 5 ℃/min to 700 ℃.
In another embodiment of the invention, the invention also provides a three-way catalyst for removing CO, NO and C in automobile exhaust x H y The use of (1). The three-way catalyst is the three-way catalyst described in the previous embodiment, or the three-way catalyst prepared by the preparation method according to the previous embodiment.
The space velocity determines the residence time of the contaminants. Under the condition of low space velocity, the pollutants are larger, the effective contact time of the pollutants and the catalyst is longer, the catalytic conversion effect of the three-way catalyst on the pollutants is more thorough, and the treatment time is correspondingly increased. In one example, the three-way catalyst is used for removing CO, NO and C in automobile exhaust at a space velocity of 30000/h-60000/h (e.g., 40000/h-50000/h) under the condition of taking treatment efficiency and catalytic efficiency of the catalyst into consideration x H y 。
The air-fuel ratio has a crucial influence on the efficiency of the three-way catalyst. The three-way catalyst has the performance of storing and releasing oxygen, so that the oxygen content can be effectively adjusted, and the air-fuel ratio operation space of the three-way catalyst is effectively widened. In one example, a three-way catalyst is used to remove CO, NO, C from automobile exhaust at an air-to-fuel ratio of 0.8-1.075 (e.g., 0.92-1.03) x H y 。
In one example, the three-way catalyst is used for removing CO, NO and C in automobile exhaust at the reaction temperature of 500-800 ℃ (for example 600-700 ℃) x H y . At 200 ℃ CO, C x H y Is preferentially adsorbed on the surface of the catalyst, during which process part of the Cu 2+ Reduction to Cu by CO + . Excess of CO, C x H y The catalyst is partially reduced to form more Ce 3+ And oxygen vacancies. When the temperature reaches 400 ℃, the catalytic performance of the catalyst on NO reaches more than 90 percent due to the improvement of the activity of Cu as an active component and the existence of oxygen vacancies for weakening N-O bonds to promote the dissociation of the active component and the oxygen vacancies. When the temperature reaches 600-700 ℃, the catalyst is coated with CO and C x H y Further reduction, i.e. more surface Ce is produced 3+ And oxygen vacancies, as is well known, surface Ce 3+ Contribute to CO and C x H y The adsorption of substances is further improved, thereby further improving the adsorption of CO and C x H y The removal efficiency of (2).
The following detailed description will be made in conjunction with the accompanying drawings. It will be appreciated by persons skilled in the art that the present invention is not limited to the specific embodiments described, but that reasonable modifications are possible in light of the teaching of the present invention.
Example 1
The three-way catalyst Cu/CeZrSnO is prepared by adopting a two-step impregnation method 2 /γ-Al 2 O 3 . The pseudoboehmite powder is heated to 800 ℃ in a muffle furnace at the heating rate of 5 ℃/min and calcined for 4 hours to obtain the gamma-Al 2 O 3 . According to Ce 4+ :Zr 4 + :Sn 4+ At a molar ratio of 0.675:0.225:0.1, Ce (NO) is added 3 ) 3 ·6H 2 O、 Zr(NO 3 ) 2 O·xH 2 O and SnCl 4 ·5H 2 Mixing O solution with total cation concentration of 0.2mol/L, adding gamma-Al 2 O 3 Magnetically stirring for 1 hour (h); then dropwise adding 25mol/L excessive ammonia water solution while stirring, and when the pH value reaches about 10, considering that the precipitation is complete; drying at 110 deg.C for 12 hr, and calcining at 700 deg.C for 4 hr to obtain light yellow CeZrSnO 2 /γ-Al 2 O 3 . Determining the optimal loading of metal Cu, and preparing Cu (m)/CeZrSnO 2 /γ-Al 2 O 3 The three-way catalyst is characterized in that m represents the mass fraction of Cu and is respectively 0 wt%, 1 wt%, 5 wt%, 7 wt% and 9 wt%. Weighing a certain amount of Cu (NO) 3 ) 2 ·3H 2 Dissolving O in ultrapure water, magnetically stirring for 15 minutes (min), pouring the mixture into a copper nitrate solution, carrying out water bath impregnation loading at the temperature of 60 ℃ for 1h, then putting the mixture into an oven for drying (110 ℃, 12h), and then roasting with a muffle furnace (700 ℃, 2h) to obtain the target three-way catalyst Cu/CeZrSnO 2 /γ- Al 2 O 3 。
Respectively Cu (0%)/CeZrSnO 2 /γ-Al 2 O 3 、Cu(1％)/CeZrSnO 2 /γ-Al 2 O 3 And Cu (5%)/CeZrSnO 2 /γ-Al 2 O 3 、Cu(7％)/CeZrSnO 2 /γ-Al 2 O 3 、Cu(9％)/CeZrSnO 2 /γ- Al 2 O 3 The catalytic activity of the three-way catalyst is evaluated in a reactor, so that the optimal loading of metal Cu is screened out.
Placing 0.5mL of catalyst in a quartz tube, placing in a tube furnace, setting the programmed temperature, setting the final reaction temperature to 600 ℃, introducing a simulated atmosphere of 10000ppm of CO, 1000ppm of NO and 3000ppm of CH (2000ppm of C) 3 H 8 +1000ppm C 3 H 6 )，0％～3％O 2 ，N 2 The flow rate of the mixed gas is 40000/h as balance gas, and timing is started at the same time; and measuring the concentrations of CO, NO and CH in the outlet gas by using a flue gas analyzer every 20 minutes, and calculating the removal rate of the three pollutants. The catalytic activity of the three-way catalyst takes the removal rate of CO, NO and CH as evaluation indexes.
Fig. 2(a), (b), and (c) are graphs illustrating the removal efficiency of CO, NO, and CH, respectively, for three-way catalysts with different copper loadings in the examples of the present invention. It can be seen from the figure that the catalytic activity of the catalysts at copper loadings of 7 wt% and 9 wt% is significantly higher than the other three catalysts. Cu/CeZrSnO with copper loadings of 7 and 9 wt% after stabilization of the reaction 2 /γ-Al 2 O 3 The catalyst has CO removing rate up to 90%, NO removing rate up to 93% and CH removing rate up to 100%.
FIG. 3 shows Cu/CeZrSnO with different Cu loading amounts 2 /γ-Al 2 O 3 XRD spectrum of catalyst. As can be seen from the figure, when the loading amount is increased from 0 wt% to 7 wt%, the characteristic peak of the Cu species is not detected, the Cu species may be highly dispersed on the surface of the catalyst, or the Cu loading amount may be too small, and exceeds the lower limit of XRD detection; when the loading amount reaches 9 wt%, a distinct CuO characteristic peak appears at both 35.5 ° and 38.7 °, because as the loading amount increases, too much copper species are aggregated on the surface of the support, which causes a decrease in the specific surface area of the catalyst and unnecessary waste of resources. As mentioned above, when the loading amount reaches 7 wt%, the loading amount of the catalyst just reaches dispersion saturation, and at the moment, the crystal grains of the catalyst are small, CuO cannot be enriched on the surface of the carrier, and the catalytic performance is optimal.
Thus, 7 wt% was selected as the optimum copper loading.
Example 2
Similar to the preparation method of the three-way catalyst in example 1, when the optimum loading amount is 7 wt%, the tin doping amount is determined first, and Cu/(Ce) is prepared by the same method 3(1-x)/4 Zr (1-x)/4 )Sn x O 2 /γ-Al 2 O 3 The three-way catalyst, wherein x represents the molar fraction of Sn doping and is respectively 0, 0.1, 0.2 and 0.3.
Respectively in Cu/(Ce) 0.75 Zr 0.25 )Sn 0 O 2 /γ-Al 2 O 3 、Cu/(Ce 0.675 Zr 0.225 )Sn 0.1 O 2 /γ-Al 2 O 3 And Cu/(Ce) 0.6 Zr 0.2 )Sn 0.2 O 2 /γ-Al 2 O 3 、Cu/(Ce 0.525 Zr 0.175 )Sn 0.3 O 2 /γ-Al 2 O 3 The catalytic activity of the three-way catalyst is evaluated in a reactor, so that the optimal doping amount of the metal Sn is screened out.
0.5mL of catalyst was placed in the stonePutting the quartz tube into a tube furnace, setting the temperature to be programmed, setting the final reaction temperature to be 600 ℃, and introducing a simulated atmosphere of 10000ppm of CO, 1000ppm of NO and 3000ppm of CH (2000ppm of C) 3 H 8 +1000ppm C 3 H 6 )，0％～3％O 2 ，N 2 The flow rate of the mixed gas is 40000/h as balance gas, and timing is started at the same time; and measuring the concentrations of CO, NO and CH in the outlet gas by using a flue gas analyzer every 20 minutes, and calculating the removal rate of the three pollutants. The catalytic activity of the three-way catalyst takes the removal rate of CO, NO and CH as evaluation indexes.
Fig. 4(a), (b), and (c) are schematic diagrams illustrating the removal efficiency curves of CO, NO, and CH with different Sn doping amounts in the embodiments of the present invention. As can be seen, Cu/(Ce) 0.675 Zr 0.225 )Sn 0.1 O 2 /γ-Al 2 O 3 The catalytic activity of the catalyst is obviously higher than that of other three catalysts, and after the reaction is stable, Cu/(Ce) 0.675 Zr 0.225 )Sn 0.1 O 2 /γ-Al 2 O 3 The removal rates of CO, NO and CH can respectively reach 92%, 89% and 100%.
Example 3
Similar to the preparation method of the three-way catalyst in example 1, when the loading of the active metal Cu and the optimum promoter (Ce) 0.75 Zr 0.25 )Sn 0.1 O 2 After determination, the optimum firing temperature of the active metal is determined. Preparation of Cu (t)/(Ce) by the same method 0.75 Zr 0.25 )Sn 0.1 O 2 /γ-Al 2 O 3 The three-way catalyst, wherein t represents the temperature of the water bath, and t is 600 ℃, 700 ℃ and 800 ℃.
Respectively taking Cu (600)/(Ce) 0.675 Zr 0.225 )Sn 0.1 O 2 /γ-Al 2 O 3 、 Cu(700)/(Ce 0.675 Zr 0.225 )Sn 0.1 O 2 /γ-Al 2 O 3 And Cu (800)/(Ce) 0.675 Zr 0.225 )Sn 0.1 O 2 /γ-Al 2 O 3 The catalyst is a three-way catalyst, and the catalytic activity of the catalyst is evaluated in a reactor, so that the optimal roasting temperature of the active metal is screened out.
Placing 0.5mL of catalyst into a quartz tube, placing the quartz tube into a tube furnace, setting the temperature to be programmed, and introducing a simulated atmosphere at the final reaction temperature of 600 ℃, 10000ppm of CO, 1000ppm of NO and 3000ppm of CH (2000ppm of C) 3 H 8 +1000ppm C 3 H 6 )，0％～3％O 2 ，N 2 The flow rate of the mixed gas is 40000/h as balance gas, and timing is started at the same time; and measuring the concentrations of CO, NO and CH in the outlet gas by using a flue gas analyzer every 20 minutes, and calculating the removal rate of the three pollutants. The catalytic activity of the three-way catalyst takes the removal rate of CO, NO and CH as evaluation indexes.
FIG. 5(a), (b) and (c) are graphs showing the removal rate of CO, NO and CH, respectively, of the catalyst at different calcination temperatures. As can be seen from the figure, the removal efficiency of the three-way catalyst calcined at 700 ℃ and 800 ℃ to CO, NO and CH is similar and is obviously higher than 600 ℃. Considering the problems of optimal removal effect and energy conservation, the optimal roasting temperature of the active metal is selected to be 700 ℃.
Example 4
Similar to the preparation method of the three-way catalyst in example 1, the same method is used to prepare Cu/CeZrO under the conditions of optimal Cu loading and optimal roasting temperature of active metal 2 /γ-Al 2 O 3 And Cu/CeZrSnO 2 /γ-Al 2 O 3 A three-way catalyst.
Preparation of Cu/CeZrO 2 /γ-Al 2 O 3 The specific operation is similar to that of the Cu/CeZrSnO 2 /γ-Al 2 O 3 Is prepared by a two-step impregnation method, wherein Ce is 4+ :Zr 4+ The molar ratio of (A) to (B) is 3: 1.
Respectively with Cu/CeZrO 2 /γ-Al 2 O 3 And Cu/CeZrSnO 2 /γ-Al 2 O 3 The sulfur resistance of the catalyst is evaluated in a reactor as a three-way catalyst, so that the optimal three-way catalyst is screened out.
Placing 0.5mL of catalyst in a quartz tube, placing the quartz tube in a tube furnace, setting the programmed temperature, and introducing a simulated atmosphere at the final reaction temperature of 600 ℃ of 10000ppm of CO, 1000ppm of NO and 3000ppm of NO CH (2000ppm C 3 H 8 +1000ppm C 3 H 6 )，0.05‰SO 2 ，0％～3％O 2 ，N 2 The flow rate of the mixed gas is 40000/h for balanced gas, and timing is started at the same time; and measuring the concentrations of CO, NO and CH in the outlet gas by using a flue gas analyzer every 20 minutes, and calculating the removal rate of the three pollutants. The catalytic activity of the three-way catalyst takes the removal rate of CO, NO and CH as evaluation indexes.
FIG. 6(a), (b) and (c) are 0.05% SO 2 The lower catalyst has a curve diagram of the removal rate of CO, NO and CH. As can be seen, Cu/CeZrO 2 /γ-Al 2 O 3 The conversion rates of CO, NO and CH are respectively reduced by 22.9 percent, 24.1 percent and 10 percent, and the conversion rate of Cu/CeZrSnO 2 /γ-Al 2 O 3 The conversion of CO, NO and CH decreased by 13.7%, 17.3% and 7%, respectively. The results show that SO 2 In the presence of p-Cu/CeZrSnO 2 /γ-Al 2 O 3 The influence of (c) is small. Sn doped catalysts exhibit SO 2 Better resistance.
Example 5
Similar to the preparation method of the three-way catalyst in example 1, the same method is used for preparing Cu/CeZrO under the conditions of optimal Cu loading and optimal roasting temperature of active metal 2 /γ-Al 2 O 3 And Cu/CeZrSnO 2 /γ-Al 2 O 3 A three-way catalyst.
FIG. 7 shows Cu/CeZrO 2 /γ-Al 2 O 3 And Cu/CeZrSnO 2 /γ-Al 2 O 3 XRD pattern of (a). As can be seen from FIG. 7, the characteristic peaks at 28.68 °, 33.28 °, 47.84 °, 56.78 ° were assigned to CeO 2 (ii) a The characteristic peaks at 37.5 degrees, 39.3 degrees, 45.7 degrees and 66.6 degrees belong to gamma-Al 2 O 3 . CeO was detected only in both catalysts 2 With gamma-Al 2 O 3 Characteristic peak of (a) no ZrO appears 2 And SnO 2 Characteristic peak of (2). This indicates that both the two assistants form a stable solid solution state and no phase segregation occurs.
FIG. 8 shows Cu/CeZrO 2 /γ-Al 2 O 3 And Cu-CeZrSnO 2 /γ-Al 2 O 3 XPS spectra of Cu 3d, Ce 3d, O1s, Sn 3d and Zr 3d of the catalysts. In the Ce ion XPS spectrum (fig. 8(a)), a total of 8 peaks appeared, which were 4 v-series peaks and 4 u-series peaks, respectively. Ce 3+ 3d 5/2 Peaks are marked as U '(903.9 eV) and V' (885.1 eV); ce 4+ 3d 3/2 The peaks are labeled U (901.1eV), U "(907.5eV), U '(916.9 eV), V (882.6eV), V" (888.6eV), and V' (898.5 eV). CeO (CeO) 2 The oxygen vacancy in the catalyst can play a role in adsorbing and activating oxygen molecules in heterogeneous reaction, and O is generated in the process of removing automobile exhaust pollutants 2 The activation of (2) is a key step in determining the reaction rate, and the increase of the adsorbed oxygen accelerates the reaction rate. With Cu/CeZrO 2 /γ-Al 2 O 3 Compared with the method, the doping of Sn improves the Ce on the surface of the catalyst 3+ And (4) content. The abundance of oxygen vacancies helps in the adsorption of reactant gases, creating conditions for the oxidation reaction. Therefore, the activity of the catalyst for oxidizing CO and CH can be greatly improved by increasing the oxygen vacancy of the catalyst. XPS spectra of Zr 3d and Sn 3d are shown in FIG. 8 (d). In Cu/CeZrO 2 /γ-Al 2 O 3 With Cu/CeZrSnO 2 /γ-Al 2 O 3 In the catalyst, the X-ray photoelectron spectrum of Zr can be divided into two parts: zr 3d 5/2 (182.4eV) and Zr 3d 3/2 (184.7eV)。Zr 3d 5/2 Characterized by a binding energy of 182.4eV with ZrO 2 The binding energy of (A) was consistent with that of 182.4eV, indicating that Zr was mainly present in the +4 oxidation state. From the XPS spectrum of Sn 3d, Cu/CeZrSnO 2 /γ-Al 2 O 3 Middle Sn 3d 5/2 The peak binding energy was 486.1eV, lower than the peak in tin oxide (486.2eV), but higher than the peak for stannous oxide binding energy 485.6 eV. This means that Sn 2+ /Sn 4+ Species existing in Cu/CeZrSnO at the same time 2 /γ-Al 2 O 3 In (1).
As shown in FIG. 8(b), the peak with the binding energy of Cu 3d XPS spectrum between 933.0-933.8eV is attributed to CuO (Cu) 2+ ) Cu2p of 3/2 (ii) a The peak with the binding energy between 932.2 and 933.1eV is assigned to Cu 2 O(Cu 1+ ) Cu2p 3/2 . Illustrating Cu in the catalyst as CuO and Cu 2 O exists in two forms.The peak at 939.8-944.1eV is Cu 2+ Is considered to be generated by the final state effect of shielding shell level vacancies by valence electrons, and is shown in Cu 2 Not observed in O and elemental Cu. The area of the fitted peak is calculated, Cu 2+ Relative content of (C) is Cu 2+ Peak area and Cu 1+ +Cu 2+ The ratio of the peak areas was estimated. As a result, it can be seen that Cu is contained in the Sn-doped catalyst 2+ Is higher than that without Sn doping. This is because both Cu and Ce have a smaller electronegativity than Sn, so that Cu undergoes a redox reaction 1+ +Sn 4+ →Cu 2+ +Sn 2+ To the right. This is consistent with the results of later quantum chemical calculations. Cu 2+ Is an active component having a main catalytic effect, and the higher the relative content of the active component, the more the oxidation-reduction capability of the catalyst is improved.
To better understand the surface of the catalyst, the O1s XPS spectra were compared in fig. 8 (c). Wherein the peak of O1s is marked as O (530.5eV) O' (531.2eV) O "(532.3eV), and O represents lattice oxygen; oxygen is adsorbed on the surface of O'; o' is weakly bonded oxygen, such as molecular water or carbonate. However, O ' is an important factor in oxidation reactions, especially CO oxidation, because O ' has a much higher oxygen mobility than O and O '. The concentration of oxygen vacancies can also be described in terms of the O '/(O "+ O' + O) ratio. From the fitting results, it can be seen that in Cu/CeZrSnO 2 /γ-Al 2 O 3 The relative content of O' on the surface of the catalyst is larger than that of Cu/CeZrO 2 /γ-Al 2 O 3 High. Apparently, by doping Sn to CeZrO 2 In the crystal lattice, the oxidation activity of CO can be improved. This and the rear face H 2 The results of TPR are consistent.
FIG. 9 shows Cu/CeZrO 2 /γ-Al 2 O 3 With Cu/CeZrSnO 2 /γ-Al 2 O 3 H of catalyst 2 -TPR spectrum. As can be seen from the figure, there are four reduction peaks in both samples, and the reduction peak at 300-400 ℃ is marked as alpha; the reduction peak at 450-550 ℃ was labeled as the beta peak; the reduction peak at 550-650 ℃ was labeled as the gamma peak; the reduction peak at 800-. Due to gamma-Al 2 O 3 High specific surface area, CuO is easily dispersed in the carrierγ-Al 2 O 3 The alpha peak is attributed to CuO species dispersed on the surface of the support. The beta peak at 465-480 ℃ belongs to a Cu species with strong interaction with the auxiliary agent, Cu/CeZrO 2 /γ- Al 2 O 3 Beta peak of the catalyst is at 486 ℃, compared with Cu/CeZrSnO 2 /γ-Al 2 O 3 The beta peak of the catalyst dropped to 467 ℃. The gamma reduction peak at 550-650 ℃ is surface layer Ce 4+ Reduction to Ce 3+ As can be seen from fig. 9, the peak value of the Sn-doped sample is significantly lower than that of the sample without Sn doping. It is known from XPS that the surface Ce is increased due to the doping of Sn 3+ Concentration to create more oxygen vacancies, Ce 4+ The concentration is reduced. The theta peak at 800-900 ℃ is attributed to the inner layer Ce 4+ Compared with a sample not doped with Sn, the surface of the Sn-doped sample and the bulk phase reduction peak both move to a low-temperature region, which shows that the doping of Sn improves the oxygen vacancy concentration of the sample, and the more oxygen defects, the faster the oxygen migration rate, and further the catalytic performance of the catalyst is improved, which is consistent with the XPS result.
To further study the oxygen mobility and oxygen vacancies of the catalyst, the present invention was applied to Cu/CeZrO 2 /γ-Al 2 O 3 With Cu/CeZrSnO 2 /γ-Al 2 O 3 Temperature programmed oxidation (O) of the catalyst 2 TPD) analysis. FIG. 10 shows Cu/CeZrO 2 /γ-Al 2 O 3 With Cu/CeZrSnO 2 /γ-Al 2 O 3 O of (A) to (B) 2 -a TPD profile. As can be seen from FIG. 10, both samples consist of three peaks, and the alpha peak at 100-200 ℃ belongs to the physically adsorbed oxygen substance, so that the acting force with the surface is weaker; adsorbing O by a beta peak and a surface oxygen vacancy at the temperature of 450-550 DEG C 2 The formed oxygen species are related, and the gamma peak at 800-950 ℃ is related to the desorption of lattice oxygen. As can be seen from fig. 10, the doping of Sn increases the β peak desorption peak area compared to the sample without Sn, indicating that the doped sample has good surface oxygen mobility, which should be related to the high concentration of oxygen vacancies observed by XPS. The increase of the oxygen migration rate of the crystal lattice can provide oxygen required by oxidation reaction under the condition of oxygen deficiency, thereby improving the catalysisCatalytic performance of the catalyst. The increase in the gamma peak desorption peak area may be due to a synergistic effect between all redox pairs, e.g. Ce 4+ /Ce 3+ And Sn 4+ /Sn 2+ . The result shows that the dopant Sn and the cerium-zirconium solid solution have a synergistic effect, which is beneficial to improving the catalytic performance of the co-doped sample.
TG analysis was used to study the type and stability of the catalyst surface sulfates after sulfur resistance testing. As can be seen from fig. 11, the thermal weight loss of the catalyst can be divided into 2 stages: the first stage is at 50-200 deg.c, and mainly includes the elimination of physically adsorbed water on the surface of the catalyst and the dewatering of surface hydroxyl radical. In the second stage, at the temperature of 500-900 ℃, the weight loss is caused by the decomposition of sulfur species and the collapse of a part of structure. Cu/CeZrO 2 /γ-Al 2 O 3 There was a distinct peak at 788 deg.C, which was attributed to CuSO 4 Decomposition of (2). But in Cu/CeZrSnO 2 /γ- Al 2 O 3 No visible peak was detected. These results indicate that Sn modification can inhibit the formation of sulfate on the surface of the catalyst active component. In conclusion, the Sn modification can reduce SO adsorbed on the surface of the active component 2 SO that SO is adsorbed 2 Is not easily adsorbed around Cu, inhibiting the formation of sulfate on the active component. The formation of sulfates (e.g., ammonium sulfate and metal sulfates) is SO 2 The main cause of catalyst deactivation in the presence of water. The doping of Sn inhibits the formation of sulfate on the surface of the catalyst, particularly on the active component Cu, and can improve the sulfur resistance of the catalyst, thereby improving the sulfur resistance of the catalyst in SO 2 Has better catalytic activity in the presence of the catalyst.
Example 6
Similar to the preparation method of the three-way catalyst in the example 1, the same method is utilized to prepare Cu/CeZrSnO under the conditions of the optimal Cu loading and the optimal active metal roasting temperature 2 /γ-Al 2 O 3 The three-way catalyst optimizes the reaction conditions under the reactor and determines the optimal space velocity.
With Cu/CeZrSnO 2 /γ-Al 2 O 3 For a three-way catalyst, the catalysis was evaluated at different space velocities in the reactorThe activity and the temperature gradient are selected from 30000/h, 40000/h, 50000/h and 60000/h, so that the optimal airspeed is screened out.
Placing 0.5mL of catalyst into a quartz tube, placing the quartz tube into a tube furnace, setting the temperature to be programmed, and introducing simulated atmosphere with the final reaction temperature of 600 ℃ respectively, 10000ppm of CO, 1000ppm of NO and 3000ppm of CH (2000ppm of C) 3 H 8 +1000ppm C 3 H 6 )，0％～3％O 2 ，N 2 The flow rates of the mixed gas are 30000/h, 40000/h, 50000/h and 60000/h respectively for balance gas, and timing is started simultaneously; and measuring the concentrations of CO, NO and CH in the outlet gas by using a flue gas analyzer every 20 minutes, and calculating the removal rate of the three pollutants. The catalytic activity of the three-way catalyst takes the removal rate of CO, NO and CH as evaluation indexes.
FIGS. 12(a), (b) and (c) show Cu/CeZrSnO at different space velocities 2 /γ-Al 2 O 3 Influence on the removal effect of CO, NO and CH. As can be seen from the figure, the space velocity is relative to the Cu/CeZrSnO 2 /γ-Al 2 O 3 The catalytic activity of the catalyst has obvious influence, and the influence on the removal efficiency of the three pollutants basically conforms to the following rules: 30000/h>40000/h> 50000/h>60000/h. That is, the smaller the space velocity, the higher the contaminant removal efficiency. Because the space velocity determines the residence time of the pollutants, the smaller the space velocity, the larger the pollutants, the longer the effective contact time of the pollutants and the catalyst, the more thorough the catalytic conversion effect of the three-way catalyst on the pollutants, but the time difference is not obvious when the space velocity is 30000/h and 40000/h, and Cu/CeZrSnO is generated when the space velocity is 40000/h 2 /γ-Al 2 O 3 The removal rates of CO, NO and CH can respectively reach 92%, 90% and 100%, so that the high catalytic activity of the catalyst can be maintained, the overall treatment efficiency is not influenced, and the cost is not increased, and therefore, the optimal space velocity is 40000/h.
Example 7
Similar to the preparation method of the three-way catalyst in the example 1, the same method is utilized to prepare Cu/CeZrSnO under the conditions of the optimal Cu loading and the optimal active metal roasting temperature 2 /γ-Al 2 O 3 The three-way catalyst optimizes the reaction conditions under the reactor,an optimum air-fuel ratio is determined.
With Cu/CeZrSnO 2 /γ-Al 2 O 3 The catalytic activity of the three-way catalyst is evaluated under different air-fuel ratios in a reactor, and the air-fuel ratio lambda is selected from 0.8, 0.9, 0.925, 0.95, 0.975, 1, 1.025, 1.05 and 1.075, so that the optimal air-fuel ratio is screened out.
Placing 0.5mL of catalyst in a quartz tube, placing the quartz tube in a tube furnace, setting a program for heating, adjusting the air-fuel ratio to be 0.8, 0.9, 0.925, 0.95, 0.975, 1, 1.025, 1.05 and 1.075 respectively, introducing a simulated atmosphere of 10000ppm of CO, 1000ppm of NO and 3000ppm of CH (2000ppm of C) 3 H 8 +1000ppm C 3 H 6 )，0％～3％O 2 ，N 2 The flow rate of the mixed gas is 40000/h as balance gas, and timing is started at the same time; and measuring the concentrations of CO, NO and CH in the outlet gas by using a flue gas analyzer every 20 minutes, and calculating the removal rate of the three pollutants. The catalytic activity of the three-way catalyst takes the removal rate of CO, NO and CH as evaluation indexes.
FIGS. 13(a) and (b) are Cu/CeZrO, respectively 2 /γ-Al 2 O 3 With Cu/CeZrSnO 2 /γ-Al 2 O 3 Schematic diagram of the oxygen concentration operating interval. As can be seen from the figure, Cu/CeZrSnO 2 /γ-Al 2 O 3 Is wider than the Cu/CeZrO 2 /γ-Al 2 O 3 The catalyst can keep the removal rate of CO, NO and CH above 85% within the air-fuel ratio of 0.92-1.03.
Example 8
Similar to the preparation method of the three-way catalyst in the example 1, the same method is utilized to prepare Cu/CeZrSnO under the conditions of the optimal Cu loading and the optimal active metal roasting temperature 2 /γ-Al 2 O 3 The three-way catalyst optimizes the reaction conditions under the reactor and determines the optimal reaction temperature.
With Cu/CeZrSnO 2 /γ-Al 2 O 3 The catalyst is a three-way catalyst, the catalytic activity of the catalyst is evaluated at different reaction temperatures in a reactor, and the temperature gradient is selected from 200, 300, 400, 500, 600 and 700 ℃, so that the optimal reaction temperature is selected。
Placing 0.5mL of catalyst in a quartz tube, placing in a tube furnace, setting program temperature rise, setting final reaction temperature to be 200, 300, 400, 500, 600 and 700 ℃, respectively, introducing simulated atmosphere of 10000ppm of CO, 1000ppm of NO and 3000ppm of CH (2000ppm of C) 3 H 8 +1000ppm C 3 H 6 )，0％～3％O 2 ，N 2 The flow rate of the mixed gas is 40000/h as balance gas, and timing is started at the same time; and measuring the concentrations of CO, NO and CH in the outlet gas by using a flue gas analyzer every 20 minutes, and calculating the removal rate of the three pollutants. The catalytic activity of the three-way catalyst takes the removal rate of CO, NO and CH as evaluation indexes.
FIGS. 14(a), (b) and (c) show the reaction temperature pairs of Cu/CeZrSnO, respectively 2 /γ-Al 2 O 3 Influence on the removal effect of CO, NO and CH. As can be seen from the figure, the temperature is corresponding to Cu/CeZrSnO 2 /γ-Al 2 O 3 The catalytic performance of the catalyst has obvious influence, and the rule of the removal efficiency of the three pollutants basically conforms to the following rule: the catalytic performance increases with increasing temperature. The catalytic performance of the catalyst reaches over 90 percent at 600 ℃ and 700 ℃, and the catalytic activity is the best. The energy consumption is saved while the pollutants are effectively removed, and the optimal reaction temperature of 600 ℃ is selected, so that the catalytic performance of the catalyst can be maintained, and the cost cannot be increased.
Although a few embodiments of the present general inventive concept have been shown and described, it will be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the general inventive concept, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A three-way catalyst is composed of the following components:
γ-Al 2 O 3 a carrier;
CeZrSnO 2 auxiliary agent, CeZrSnO 2 The auxiliary agent enters the gamma-Al through a dipping mode 2 O 3 In a carrier to form CeZrSnO 2 /γ-Al 2 O 3 A complex; and
active metal copper, wherein the active metal copper enters the CeZrSnO through a dipping mode 2 /γ-Al 2 O 3 In a complex.
2. The three-way catalyst of claim 1,
sn in CeZrSnO 2 The mole ratio of the auxiliary agent is 5-30%,
the molar ratio of Ce to Zr is 3: 1.
3. the three-way catalyst according to claim 1 or 2, wherein,
the mass of the copper in the three-way catalyst accounts for 5-10 wt%,
the gamma-Al 2 O 3 Carrier and CeZrSnO 2 The mass ratio of the auxiliary agent is 25 (2-8).
4. A method of making the three-way catalyst of any one of claims 1-3, comprising:
providing gamma-Al 2 O 3 A carrier;
providing a first mixed solution of a cerium source, a zirconium source, and a tin source;
subjecting the gamma-Al to 2 O 3 Mixing a carrier and the first mixed solution to form a second mixed solution, adding an ammonia water solution into the second mixed solution for impregnation and loading to obtain a first reactant, and roasting the first reactant to obtain CeZrSnO 2 /γ-Al 2 O 3 A complex;
CeZrSnO 2 /γ-Al 2 O 3 Mixing the composite and a solution of a copper source, carrying out water bath impregnation loading to obtain a second reactant, and roasting the second reactant to obtain the Cu/CeZrSnO 2 /γ-Al 2 O 3 The three-way catalyst of (1).
5. The production method according to claim 4,
Cu/CeZrSnO 2 /γ-Al 2 O 3 the three-way catalyst of (a) is passed through twoPrepared by a dipping method.
6. The production method according to claim 4 or 5,
the cerium source comprises at least one of cerium nitrate and hydrate thereof, cerium chloride and hydrate thereof, ammonium cerium nitrate and hydrate thereof, and ammonium cerium sulfate and hydrate thereof;
the zirconium source comprises at least one of zirconium chloride and hydrates thereof, zirconyl nitrate and hydrates thereof, and zirconium acetate and hydrates thereof;
the tin source comprises at least one of tin nitrate and hydrate thereof, tin tetrachloride and hydrate thereof, and tin acetate and hydrate thereof;
the copper source comprises at least one of copper nitrate and hydrate thereof, and copper chloride and hydrate thereof.
7. The production method according to claim 6, wherein,
in providing gamma-Al 2 O 3 In the process of the carrier, the pseudo-boehmite powder is calcined for 3 to 5 hours at the temperature of 700 to 900 ℃.
8. The production method according to claim 7, wherein,
in the process of obtaining the first reactant, adding 20-30mol/L ammonia water solution into the second mixed solution under the condition of stirring, and obtaining the first reactant when the pH value reaches 9-12;
in the process of roasting the first reactant, the first reactant is dried at the temperature of 105-120 ℃ for 10-15 hours and then roasted at the temperature of 600-800 ℃ for 2-5 hours.
9. The production method according to claim 8,
in the process of obtaining the second reactant, CeZrSnO 2 /γ-Al 2 O 3 Mixing the compound with the solution of the copper source, and then carrying out water bath impregnation loading at the temperature of 50-80 ℃ for 0.5-3 hours;
in the process of roasting the second reactant, the second reactant is dried at 120 ℃ of 105 ℃ for 10-15 hours and then roasted at 800 ℃ of 600 ℃ for 1-3 hours.
10. Three-way catalyst for removing CO, NO and C in automobile exhaust x H y The three-way catalyst of any one of claims 1 to 3, or the three-way catalyst prepared by the preparation method of any one of claims 4 to 9,
wherein the three-way catalyst is used for removing CO, NO and C in the automobile exhaust at the space velocity of 30000/h-60000/h, the air-fuel ratio of 0.8-1.075 and the reaction temperature of 500-800 DEG C x H y 。
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