CN114984969B - 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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- CN114984969B CN114984969B CN202210823374.8A CN202210823374A CN114984969B CN 114984969 B CN114984969 B CN 114984969B CN 202210823374 A CN202210823374 A CN 202210823374A CN 114984969 B CN114984969 B CN 114984969B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 189
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000010949 copper Substances 0.000 claims abstract description 163
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 130
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 67
- 229910052802 copper Inorganic materials 0.000 claims abstract description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 238000005470 impregnation Methods 0.000 claims abstract description 13
- 238000007598 dipping method Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 32
- 239000000376 reactant Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000011068 loading method Methods 0.000 claims description 27
- 239000000446 fuel Substances 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 229910052684 Cerium Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052718 tin Inorganic materials 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 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
- 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 6
- 238000003756 stirring Methods 0.000 claims description 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 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 4
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- 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 3
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 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 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 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 3
- 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 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-O azanium;hydron;hydroxide Chemical compound [NH4+].O VHUUQVKOLVNVRT-UHFFFAOYSA-O 0.000 claims 4
- WTVAYLQYAWAHAX-UHFFFAOYSA-J cerium(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Ce+4] WTVAYLQYAWAHAX-UHFFFAOYSA-J 0.000 claims 4
- ATYZRBBOXUWECY-UHFFFAOYSA-N zirconium;hydrate Chemical compound O.[Zr] ATYZRBBOXUWECY-UHFFFAOYSA-N 0.000 claims 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 62
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 53
- 239000001301 oxygen Substances 0.000 abstract description 53
- 230000003197 catalytic effect Effects 0.000 abstract description 48
- 230000001965 increasing effect Effects 0.000 abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 abstract description 10
- 239000011593 sulfur Substances 0.000 abstract description 10
- 238000003860 storage Methods 0.000 abstract description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 118
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 71
- 239000007789 gas Substances 0.000 description 24
- 239000003344 environmental pollutant Substances 0.000 description 16
- 231100000719 pollutant Toxicity 0.000 description 16
- 230000000694 effects Effects 0.000 description 13
- 230000009467 reduction Effects 0.000 description 13
- 238000006722 reduction reaction Methods 0.000 description 13
- 150000004677 hydrates Chemical class 0.000 description 12
- 239000000356 contaminant Substances 0.000 description 10
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000001354 calcination Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000003546 flue gas Substances 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 230000008901 benefit Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 239000013618 particulate matter Substances 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 4
- 230000010718 Oxidation Activity Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 230000002776 aggregation Effects 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
- 239000001166 ammonium sulphate Substances 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 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
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 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
- 150000001768 cations Chemical class 0.000 description 1
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001879 copper Chemical class 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 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
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process 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
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 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
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
Landscapes
- 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 and a preparation method and application thereof, and belongs to the field of automobile exhaust treatment. The three-way catalyst consists of the following components: gamma-Al 2 O 3 A carrier; ceZrSnO 2 Auxiliary agent, the CeZrSnO 2 The auxiliary agent enters the gamma-Al through an impregnation mode 2 O 3 In a carrier to form CeZrSnO 2 /γ‑Al 2 O 3 A complex; and active metal copper which enters the CeZrSnO through a dipping mode 2 /γ‑Al 2 O 3 In the complex. The three-way catalyst of the invention is 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 efficient removal of CO, NO and C in the 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
Currently, automobiles have become the primary means of transportation for people to travel. However, the pollutant discharged by the automobile can potentially affect the ambient air while being convenient for people to travel. The total emission of four pollutants of the motor vehicle in the whole country for one year is 1593.0 ten thousand according to statisticsTons. In particular carbon monoxide (CO), hydrocarbons (CH or C x H y ) Nitrogen Oxides (NO) x ) The Particulate Matter (PM) emissions were 769.7 ten thousand tons, 190.2 ten thousand tons, 626.3 ten thousand tons, and 6.8 ten thousand tons, respectively. In particular, automobiles are major contributors to the total pollutant emissions, which emit carbon monoxide (CO), hydrocarbons (CH), nitrogen oxides (NO x ) And Particulate Matter (PM) exceeding 90% of the total vehicle emissions. These contaminants not only destroy the natural ecological environment, but also endanger the physical health of humans.
In practice, three-way catalysts can be used to remove pollutants, such as CO, NO, C, from automobile exhaust x H y Etc. However, the currently commercial three-way catalyst has higher catalytic efficiency, but is extremely easy to generate sulfur poisoning and deactivate, is not easy to regenerate and needs to be replaced frequently, so that the use cost is increased, and the pollutant removal efficiency is reduced.
Disclosure of Invention
In order to solve at least one of the problems and defects in the prior art, embodiments of the present invention provide a three-way catalyst and a preparation method thereof, and the three-way catalyst is used for removing CO, NO and C in automobile exhaust x H y Is used in the field of applications.
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, the CeZrSnO 2 The auxiliary agent enters the gamma-Al through an impregnation mode 2 O 3 In a carrier to form CeZrSnO 2 /γ-Al 2 O 3 A complex; and active metal copper which enters the CeZrSnO through a dipping mode 2 /γ-Al 2 O 3 In the complex.
According to another aspect of the present invention, there is provided a method for preparing the three-way catalyst according to the above embodiment, including: 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 the carrier and the first mixed solution to form a second mixed solution, and mixing the second mixed solution into the second mixed solutionAdding ammonia water solution into the mixed solution to carry out impregnation 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 compound is mixed with a copper source solution to be carried out water bath dipping load to obtain a second reactant, and the second reactant is roasted to obtain Cu/CeZrSnO 2 /γ- Al 2 O 3 Is a three-way catalyst.
According to another aspect of the invention, a three-way catalyst for removing CO, NO and C in automobile exhaust is provided x H y The three-way catalyst is the three-way catalyst according to the previous embodiment or the three-way catalyst prepared by the preparation method according to the previous embodiment, wherein the three-way catalyst is used for removing CO, NO and C in automobile exhaust at a space velocity of 30000/h-60000/h, an air-fuel ratio of 0.8-1.075 and a reaction temperature of 500-800 DEG C x H y 。
The three-way catalyst according to the invention, as well as the preparation method and the application thereof, have at least one of the following advantages:
(1) The three-way catalyst of the invention is CeZrSnO 2 The existence of the auxiliary agent (such as Sn) improves the sulfur resistance of the three-way catalyst and prolongs the service life of the catalyst;
(2) The three-way catalyst of the invention is CeZrSnO 2 The auxiliary agent (such as Sn) has excellent oxygen storage and release functions, can effectively adjust the oxygen content, and effectively widens the air-fuel ratio operation space of the three-way catalyst;
(3) The three-way catalyst of the invention is CeZrSnO 2 The presence of the auxiliary agent (e.g., the action of Sn) increases the catalytic activity of the active component;
(4) The three-way catalyst disclosed by the invention uses copper with relatively low cost as an active component, so that the cost of the three-way catalyst is reduced, and the industrial large-scale application is facilitated;
(5) The three-way catalyst of the invention uses gamma-Al 2 O 3 A carrier having a high heightThe specific surface area and the high adsorption capacity of the catalyst are favorable for highly dispersing and loading the active components on the carrier;
(6) The preparation method of the invention has simple preparation process and can effectively remove CO, NO and C in the automobile exhaust with low cost x H y The purpose of (2);
(7) The three-way catalyst has simple application process and can efficiently realize CO, NO and C in automobile exhaust x H y Is removed.
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, in which:
FIG. 1 illustrates a method of preparing a three-way catalyst according to an embodiment of the present invention;
FIGS. 2 (a), (b) and (c) are respectively three-way catalysts Cu/CeZrSnO at different copper loadings in examples of the invention 2 /γ-Al 2 O 3 Schematic diagrams of efficiency curves of catalytic conversion of CO (a), NO (b) and CH (c);
FIG. 3 is a graph of Cu/CeZrSnO with different Cu loadings in an embodiment of the invention 2 /γ-Al 2 O 3 XRD patterns of the catalyst;
FIGS. 4 (a), (b) and (c) are schematic views showing the effect of different Sn doping amounts on the catalyst activity in the examples of the present invention;
FIGS. 5 (a), (b) and (c) are Cu/CeZrSnO at different firing temperatures in the examples of the present invention 2 /γ-Al 2 O 3 Schematic diagram of the efficiency of catalytic conversion of CO, NO and CH;
FIGS. 6 (a), (b) and (c) are each at 0.05% SO 2 Cu/CeZrO under conditions 2 /γ-Al 2 O 3 And Cu/CeZrSnO of the embodiment of the invention 2 /γ-Al 2 O 3 Schematic of the efficiency of the catalyst to catalytically convert CO, NO and CH;
FIG. 7 is a Cu/CeZrO 2 /γ-Al 2 O 3 And Cu/CeZrSnO of the embodiment of the invention 2 /γ-Al 2 O 3 An XRD pattern of (a);
FIGS. 8 (a), (b), (c) and (d) are XPS spectra of (a) Ce 3d, (b) Cu2p, (c) O1s, (d) Zr 3d and Sn 3d, respectively, in the three-way catalyst of the example of the present invention;
FIG. 9 is a Cu/CeZrO 2 /γ-Al 2 O 3 And Cu/CeZrSnO of the embodiment of the invention 2 /γ-Al 2 O 3 H of (2) 2 -a TPR profile;
FIG. 10 is a Cu/CeZrO 2 /γ-Al 2 O 3 And Cu/CeZrSnO of the embodiment of the invention 2 /γ-Al 2 O 3 O of (2) 2 -TPD profile;
FIG. 11 is SO 2 TG curve of the three-way catalyst of the example of the invention after treatment;
FIGS. 12 (a), (b) and (c) are Cu/CeZrSnO of an embodiment of the invention at different airspeeds, respectively 2 /γ-Al 2 O 3 Schematic diagram of the efficiency of catalytic conversion of CO, NO and CH;
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 diagram of (2);
FIGS. 14 (a), (b) and (c) are Cu/CeZrSnO of an embodiment of the invention at different reaction temperatures 2 /γ- Al 2 O 3 The efficiency of catalytic conversion of CO, NO and CH is shown schematically.
Detailed Description
The technical scheme of the invention is further specifically described below through examples and with reference to the accompanying drawings. In the specification, the same or similar reference numerals denote the same or similar components. The following description of embodiments of the present invention with reference to the accompanying drawings is intended to illustrate the general inventive concept and should not be taken as limiting the invention.
In an embodiment of the present invention, a three-way catalyst is provided. The three-way catalyst consists of 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 an impregnation mode 2 O 3 Carrier bodyTo form CeZrSnO 2 /γ-Al 2 O 3 A complex. The active metal copper enters the CeZrSnO through a dipping mode 2 /γ-Al 2 O 3 In the complex. That is, the three-way catalyst of the invention is composed of Cu/CeZrSnO 2 /γ-Al 2 O 3 。
The three-way catalyst of the embodiment of the invention adopts gamma-Al 2 O 3 As a carrier by reacting 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 are loaded on 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 and release performance, so that the catalytic activity of the three-way catalyst is increased and the service life of the three-way catalyst is prolonged.
Specifically, ceZrSnO in the three-way catalyst of the present invention 2 The auxiliary agent (specifically, modification of Sn) can improve the sulfur resistance of the three-way catalyst. Sn modification can reduce SO adsorbed on the surface of the active component (Cu) 2 SO that SO 2 Is not easy to adsorb around Cu and inhibits the formation of sulfate on the active component. The formation of sulphates (e.g. ammonium sulphate and metal sulphates) is SO 2 The main cause of catalyst deactivation in the presence of the catalyst. The doping of Sn inhibits the formation of sulfate on the catalyst surface, particularly on the active component Cu, thus improving the sulfur resistance of the three-way catalyst, thereby reducing SO 2 Has better catalytic activity in the presence.
CeZrSnO in the three-way catalyst of the invention 2 Auxiliaries (in particular, modifications of Sn) allow the three-way catalyst to be used in a wider operating space of oxygen concentration, for example for the removal of CO, NO, C in automobile exhaust x H y . Tin (Sn) has both +2 and +4 valence states, so that the doping of Sn is a doping of a variable valence ion, which causes the generation of extrinsic oxygen vacancies. While extrinsic oxygen vacancies lead to the generation of trivalent Ce, they satisfy (1-a) CeO 2 + aSnO→Ce 1-a Sn a O 2-a +vo, where Vo is an oxygen vacancy. So the doping of Sn improves Ce on the surface of the catalyst 3+ Content and generates rich oxygen vacancies. The abundant oxygen vacancies help the adsorption of reactant gases, creating conditions for the oxidation reaction. Thus, the improvement of the oxygen vacancies of the catalyst can greatly improve the oxidation activity of CO and CH. That is, ceZrSnO 2 The auxiliary agent has the function of oxygen storage and oxygen release. The three-way catalyst can exert better three-way catalytic performance under the condition of the small range of the theoretical air-fuel ratio, so that the actual air-fuel ratio has a critical influence on the efficiency of the three-way catalyst, and the catalytic auxiliary agent has the functions of oxygen storage and oxygen release, can effectively adjust the oxygen content, and further effectively widens the air-fuel ratio operation space of the three-way catalyst.
CeZrSnO in the three-way catalyst of the invention 2 The promoter (specifically, modification of Sn) also improves the catalytic efficiency of the metal active component. This is because Cu and Ce are less electronegative than Sn, resulting in redox Cu 1+ +Sn 4+ →Cu 2+ +Sn 2+ To the right, thereby increasing Cu 2+ Is contained in the composition. Cu (Cu) 2+ The catalyst is an active component with a main catalytic effect, and the higher the relative content is, the more is the contribution to the improvement of the oxidation-reduction capability of the catalyst, so that the catalytic efficiency of the metal active component is improved.
The three-way catalyst of the invention 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 further beneficial to highly dispersing and loading the active component on the carrier; furthermore, gamma-Al 2 O 3 The carrier has a highly porous structure, and many unit cell gaps and defects exist in the crystal, so the carrier has higher activity.
In addition, the three-way catalyst provided by the embodiment of the invention adopts copper as an active ingredient, and compared with common noble metals, the Cu has low cost, so that the cost of the three-way catalyst is effectively reduced.
In one example, sn is CeZrSnO 2 The mole ratio of the auxiliary agent is 5% -30%, preferably 8% -15%, more preferably 10%. When the doping amount of Sn is 10%, ceZrO 2 Solid solution will generate crystal latticeDefects, widening oxygen migration channels and enhancing oxygen migration capacity. CeZrO with increasing Sn doping 2 The degree of cubic distortion of the solid solution is increased, the stability of the formed cubic phase is reduced, the kinetics is unfavorable for oxygen migration, meanwhile, the Ce content is reduced, the oxygen storage capacity of the auxiliary agent is insufficient, enough oxygen cannot be provided for oxidation-reduction reaction, and the catalytic performance is reduced.
In one example, in CeZrSnO 2 In the auxiliary agent, the mole ratio of Ce to Zr is (2-5): 1, preferably 3:1.
by selecting Sn in CeZrSnO 2 The three-way catalyst having excellent exhaust gas removal effect can be obtained by the mole ratio of the auxiliary agent and the mole ratio of Ce to Zr. For example, in CeZrSnO 2 In the auxiliary agent, the molar ratio of cerium, zirconium and tin, n (Ce), n (Zr) and n (Sn) is selected to be 0.675:0.225:0.1; the three-way catalyst comprising the auxiliary agent has good effect of removing CO, NO and CH in automobile exhaust, and the removal rates can reach 92%, 95% and 100% respectively.
In one example, the copper is present in the three-way catalyst in a mass ratio of 1wt% to 10wt%, preferably 5wt wt% to 10wt%, more preferably 7wt% to 9wt%. Copper is the main active component in three-way catalysts. As the copper loading increases, the catalytic activity will be continuously improved; however, when the copper loading is excessive, too many copper species can aggregate on the surface of the carrier, and the agglomeration can cause the reduction of the specific surface area of the catalyst and unnecessary waste of resources.
In one example, gamma-Al 2 O 3 Carrier and CeZrSnO 2 The mass ratio of the auxiliary agent is 25 (2-8), preferably 25 (4-6). The mass ratio of the carrier to the auxiliary agent is selected, so that 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 preparing 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 Carrier and method for producing the sameThe first mixed solution is mixed to form a second mixed solution, alkaline solution (such as ammonia water solution) is added into the second mixed solution for immersion loading to obtain a first reactant, and the first reactant is roasted to remove water 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 compound with a copper source solution, carrying out water bath impregnation loading to obtain a second reactant, and roasting the second reactant to decompose the impregnated copper source to obtain Cu/CeZrSnO 2 /γ- Al 2 O 3 Is a three-way catalyst.
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 has the advantages of simple process flow, environment friendliness and obvious cost advantage.
In one example, gamma-Al is provided 2 O 3 During the carrier process, the pseudo-boehmite powder (e.g., in a muffle furnace) is calcined at 700 ℃ -900 ℃ (e.g., 800 ℃) for 3-5 hours (e.g., 4 hours). The process can remove water from aluminum oxide to obtain active aluminum oxide, i.e. gamma-Al 2 O 3 . For example, pseudo-boehmite powder was calcined in a muffle furnace at a temperature increase rate of 5 ℃ per minute to 800 ℃ for 4 hours.
In an example, the cerium source includes at least one of cerium nitrate and its hydrates, cerium chloride and its hydrates, ammonium cerium nitrate and its hydrates, ammonium cerium sulfate and its hydrates.
In one example, the zirconium source includes at least one of zirconium chloride and its hydrates, zirconyl nitrate and its hydrates, zirconium acetate and its hydrates.
In one example, the tin source includes at least one of tin nitrate and its hydrates, tin tetrachloride and its hydrates, tin acetate and its hydrates.
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 the process of obtaining the first reactant, 20 to 30mol/L (e.g., 25 mol/L) of an aqueous ammonia solution 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., the pH reaches 10).
During calcination of the first reactant, the first reactant is dried at 105-120℃ (e.g., 110℃) for 10-15 hours (e.g., 11-13 hours, and more e.g., 12 hours), and then calcined at 600-800℃ (e.g., in a muffle furnace) for 2-5 hours (e.g., 3-4 hours). This removes nitrogen-containing species and moisture from the first reactant.
Alternatively, the first reactant may be ground to a powder after being dried, and then calcined in a muffle furnace at a temperature rise rate of 5 ℃ per minute to 700 ℃ for 4 hours.
In one example, the copper source includes at least one of copper nitrate and its hydrates, copper chloride and its hydrates.
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.
During the process of obtaining the second reactant, ceZrSnO 2 /γ-Al 2 O 3 The composite is mixed with a solution of copper source and then loaded in a water bath at a temperature of 50-80 c (e.g., 60-70 c) for a period of 0.5-3 hours (e.g., 1-2 hours). This allows the metal active component to be supported on the carrier.
During calcination of the second reactant, the second reactant is dried at 105-120℃ (e.g., 110℃) for 10-15 hours (e.g., 11-13 hours) and then calcined at 600-800℃ (e.g., 700℃) for 1-3 hours (e.g., 1.5-2.5 hours). This may cause the copper salt species to decompose.
Alternatively, the second reactant may be ground to a powder after being dried, and then calcined in a muffle furnace at a temperature rise rate of 5 ℃ per minute to 700 ℃ for 2 hours.
In yet another embodiment of the present invention, there is also provided a three-way catalyst for use in removing automobile exhaustCO、 NO、C x H y Is used in the field of applications. 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.
Space velocity determines the residence time of the contaminant. At a smaller space velocity, the pollutant is larger, the longer the effective contact time between the pollutant and the catalyst is, the more thorough the catalytic conversion of the pollutant by the three-way catalyst is, but the treatment time is correspondingly increased. In one example, the three-way catalyst is used to remove CO, NO, and C from automobile exhaust at a space velocity of 30000/h-60000/h (e.g., 40000/h-50000/h) with a compromise between treatment efficiency and catalytic efficiency of the catalyst x H y 。
The air-fuel ratio has a critical influence on the efficiency of the three-way catalyst. The three-way catalyst has the property of oxygen storage and release, so that the oxygen content can be effectively regulated, and the air-fuel ratio operation space of the three-way catalyst can be effectively widened. In one example, a three-way catalyst is used to remove CO, NO, and C from automobile exhaust at an air-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 to remove CO, NO, and C from automobile exhaust at a reaction temperature of 500-800 ℃ (e.g., 600-700 ℃) x H y . At 200 ℃, CO, C x H y Preferentially adsorb on the surface of the catalyst, during which a part of Cu 2+ Reduction of CO to Cu + . Excessive CO, C x H y Partial reduction of the catalyst to form more Ce 3+ And oxygen vacancies. When the temperature reaches 400 ℃, the N-O bonds are weakened to promote the dissociation of the active component Cu due to the improvement of the activity of the active component Cu and the existence of oxygen vacancies, so that the catalytic performance of the active component Cu to NO reaches more than 90 percent. When the temperature reaches 600-700 ℃, the catalyst is coated with CO and C x H y Further reduction, i.e. producing more surface Ce 3+ And oxygen vacancies, surface Ce, as is well known 3+ Contributing to CO and C x H y Adsorption of substances, thereby further improving the adsorption of substances on CO and C x H y Is not limited, and the removal efficiency of the same is improved.
The following detailed description will proceed with reference being made to specific embodiments, and to the accompanying drawings. It will be appreciated by persons skilled in the art that the invention is not limited to the specific embodiments described and that reasonable modifications may be made after understanding the concepts of the invention.
Example 1
Preparation of three-way catalyst Cu/CeZrSnO by two-step impregnation method 2 /γ-Al 2 O 3 . Raising the temperature of pseudo-boehmite powder to 800 ℃ in a muffle furnace at a heating rate of 5 ℃/min, and calcining for 4 hours to obtain gamma-Al 2 O 3 . According to Ce 4+ :Zr 4 + :Sn 4+ Molar ratio=0.675:0.225:0.1 Ce (NO 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 ammonia water solution with an excessive amount of 25mol/L while stirring, and considering that the precipitation is complete when the pH value reaches about 10; drying at 110deg.C for 12 hr, and roasting at 700deg.C for 4 hr to obtain yellowish CeZrSnO 2 /γ-Al 2 O 3 . Determining the optimal load of metal Cu, and preparing Cu (m)/CeZrSnO 2 /γ-Al 2 O 3 Three-way catalyst, wherein m represents the mass fraction of Cu, and is 0wt%, 1wt%, 5wt%, 7wt% and 9wt% respectively. Weighing a certain amount of Cu (NO) 3 ) 2 ·3H 2 Dissolving O in ultrapure water, magnetically stirring for 15 min, pouring the mixture into copper nitrate solution, carrying out water bath impregnation loading at 60 ℃ for 1h, then putting the mixture into an oven for drying (110 ℃ for 12 h), and then roasting with a muffle furnace (700 ℃ for 2 h) 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 was evaluated in the reactor for a three-way catalyst, thereby screening the optimum loading of metallic Cu.
Placing 0.5mL of catalyst in a quartz tube, placing in a tube furnace, setting temperature programming, final reaction temperature of 600deg.C, introducing simulated atmosphere, 10000ppm CO,1000ppm NO,3000ppm CH (2000 ppm C) 3 H 8 +1000ppm C 3 H 6 )，0％～3％O 2 ，N 2 For balancing the gas, the flow rate of the mixed gas is 40000/h, and timing is started at the same time; the concentration of CO, NO, CH in the outlet gas was measured with a flue gas analyzer every 20 minutes, and the removal rates of the three contaminants were calculated. The catalytic activity of the three-way catalyst takes the removal rate of CO, NO and CH as an evaluation index.
Fig. 2 (a), (b) and (c) are schematic diagrams of the removal efficiency curves of the three-way catalyst for CO, NO and CH at different copper loadings in the examples of the present invention. From the figure, the catalytic activity of the copper-supported catalysts at 7wt% and 9wt% was significantly higher than the other three catalysts. After stabilization of the reaction, 7wt% and 9wt% copper loaded Cu/CeZrSnO 2 /γ-Al 2 O 3 The catalyst has a CO removal rate of 90%, a NO removal rate of 93% and a CH removal rate of 100%.
FIG. 3 is a graph of Cu/CeZrSnO with different Cu loadings 2 /γ-Al 2 O 3 XRD spectrum of the catalyst. As can be seen from the graph, when the loading is increased from 0wt% to 7wt%, no characteristic peak of Cu species is detected, which may be highly dispersed on the catalyst surface, or too little Cu loading, exceeding the XRD detection lower limit; when the loading reaches 9wt%, obvious CuO characteristic peaks appear at 35.5 ° and 38.7 °, because with the increase of the loading, excessive copper species can aggregate on the surface of the carrier, and the aggregation can cause the reduction of the specific surface area of the catalyst and the unnecessary waste of resources. As described above, when the loading reaches 7wt%, the catalyst loading just reaches dispersion saturation, and at this time, catalyst grains are smaller, enrichment of CuO on the surface of the carrier does not occur, and the catalytic performance is optimal.
Thus 7wt% was chosen as the optimal copper loading.
Example 2
Similar to the preparation method of the three-way catalyst of the above example 1, when the optimum loading is determined to be 7wt%, the tin doping amount is first determined, 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 A three-way catalyst, wherein x represents the mole fraction of Sn doping, 0,0.1,0.2,0.3 respectively.
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 was evaluated in the reactor as a three-way catalyst, thereby screening the optimum doping amount of metallic Sn.
Placing 0.5mL of catalyst in a quartz tube, placing in a tube furnace, setting temperature programming, final reaction temperature of 600deg.C, introducing simulated atmosphere, 10000ppm CO,1000ppm NO,3000ppm CH (2000 ppm C) 3 H 8 +1000ppm C 3 H 6 )，0％～3％O 2 ，N 2 For balancing the gas, the flow rate of the mixed gas is 40000/h, and timing is started at the same time; the concentration of CO, NO, CH in the outlet gas was measured with a flue gas analyzer every 20 minutes, and the removal rates of the three contaminants were calculated. The catalytic activity of the three-way catalyst takes the removal rate of CO, NO and CH as an evaluation index.
Fig. 4 (a), (b), and (c) are schematic diagrams of graphs of different Sn doping amounts versus CO, NO, and CH removal efficiency, respectively, in the embodiments of the present invention. From the figure, 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 the other three catalysts, and Cu/(Ce) after the reaction is stable 0.675 Zr 0.225 )Sn 0.1 O 2 /γ-Al 2 O 3 The removal rates of CO, NO and CH can reach 92%, 89% and 100% respectively.
Example 3
Similar to the preparation method of the three-way catalyst in the example 1, when the active metal Cu is loaded and the optimum auxiliary agent (Ce 0.75 Zr 0.25 )Sn 0.1 O 2 After the determination, the optimal 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 Three-way catalyst, wherein t represents the water bath temperature, t is 600 ℃, 700 ℃ and 800 ℃.
Respectively by 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 catalytic activity of the three-way catalyst was evaluated in a reactor to select the optimum active metal calcination temperature.
Placing 0.5mL of catalyst in a quartz tube, placing in a tube furnace, setting temperature programming, final reaction temperature of 600deg.C, introducing simulated atmosphere, 10000ppm CO,1000ppm NO,3000ppm CH (2000 ppm C) 3 H 8 +1000ppm C 3 H 6 )，0％～3％O 2 ，N 2 For balancing the gas, the flow rate of the mixed gas is 40000/h, and timing is started at the same time; the concentration of CO, NO, CH in the outlet gas was measured with a flue gas analyzer every 20 minutes, and the removal rates of the three contaminants were calculated. The catalytic activity of the three-way catalyst takes the removal rate of CO, NO and CH as an evaluation index.
FIGS. 5 (a), (b) and (c) are graphs showing the removal rates of CO, NO and CH by the catalyst at different calcination temperatures. The graph shows that the three-way catalyst baked at 700 ℃ and 800 ℃ has similar removal efficiency of CO, NO and CH and is obviously higher than 600 ℃. The optimal removal effect and the energy saving problem are considered, and 700 ℃ is selected as the optimal roasting temperature of the active metal.
Example 4
Similar to the preparation method of the three-way catalyst of the above example 1, cu/CeZrO was prepared under the conditions of optimal Cu loading and optimal calcination temperature of active metal by the same method 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 Specific operation and Cu/CeZrSnO 2 /γ-Al 2 O 3 Is prepared similarly by a two-stage impregnation method, wherein Ce 4+ :Zr 4+ The molar ratio of (2) is 3:1.
Respectively by Cu/CeZrO 2 /γ-Al 2 O 3 And Cu/CeZrSnO 2 /γ-Al 2 O 3 The three-way catalyst was evaluated for sulfur resistance in the reactor, and thus the optimal three-way catalyst was selected.
Placing 0.5mL of catalyst in a quartz tube, placing in a tube furnace, setting temperature programming, final reaction temperature of 600deg.C, introducing simulated atmosphere, 10000ppm CO,1000ppm NO,3000ppm CH (2000 ppm C) 3 H 8 +1000ppm C 3 H 6 )，0.05‰SO 2 ，0％～3％O 2 ，N 2 For balancing the gas, the flow rate of the mixed gas is 40000/h, and timing is started at the same time; the concentration of CO, NO, CH in the outlet gas was measured with a flue gas analyzer every 20 minutes, and the removal rates of the three contaminants were calculated. The catalytic activity of the three-way catalyst takes the removal rate of CO, NO and CH as an evaluation index.
FIGS. 6 (a), (b) and (c) are each 0.05% SO 2 The lower catalyst has a schematic diagram of the removal rate of CO, NO and CH. As can be seen from the figure, cu/CeZrO 2 /γ-Al 2 O 3 The conversion of CO, NO and CH is reduced by 22.9%, 24.1% and 10%, respectively, cu/CeZrSnO 2 /γ-Al 2 O 3 The conversion of CO, NO and CH was reduced by 13.7%, 17.3% and 7%, respectively. The results indicate that SO 2 Is to Cu/CeZrSnO 2 /γ-Al 2 O 3 Less of an effect of (a) is present.Sn doped catalysts exhibit a specific SO activity 2 Better resistance.
Example 5
Similar to the preparation method of the three-way catalyst of the above example 1, cu/CeZrO was prepared under the conditions of optimal Cu loading and optimal calcination temperature of active metal by the same method 2 /γ-Al 2 O 3 And Cu/CeZrSnO 2 /γ-Al 2 O 3 A three-way catalyst.
FIG. 7 is a Cu/CeZrO 2 /γ-Al 2 O 3 And Cu/CeZrSnO 2 /γ-Al 2 O 3 Is a XRD pattern of (C). As can be seen from fig. 7, characteristic peaks at 28.68 °, 33.28 °, 47.84 °, 56.78 ° are attributed to CeO 2 The method comprises the steps of carrying out a first treatment on the surface of the Characteristic peaks at 37.5 °, 39.3 °, 45.7 °, 66.6 ° are ascribed to γ -Al 2 O 3 . Only CeO was detected by both catalysts 2 With gamma-Al 2 O 3 Is free of ZrO 2 And SnO 2 Is a characteristic peak of (2). This indicates that both adjuvants form a stable solid solution state and that no phase segregation occurs.
FIG. 8 is a Cu/CeZrO 2 /γ-Al 2 O 3 With Cu/CeZrSnO 2 /γ-Al 2 O 3 XPS spectra of Cu 3d, ce 3d, O1s, sn 3d and Zr 3d of the catalyst. In the Ce ion XPS spectrum (fig. 8 (a)), a total of 8 peaks appear, 4 v-series peaks and 4 u-series peaks, respectively. Ce (Ce) 3+ 3d 5/2 Peaks are labeled U '(903.9 eV) and V' (885.1 eV); ce (Ce) 4+ 3d 3/2 Peaks are labeled U (901.1 eV), U "(907.5 eV), U '" (916.9 eV), V (882.6 eV), V "(888.6 eV) and V'" (898.5 eV). CeO (CeO) 2 Oxygen vacancies in the catalyst can play a role in adsorbing and activating oxygen molecules in heterogeneous reaction, and O is removed in the process of removing pollutants in automobile exhaust 2 Is a key step in determining the reaction rate, and the increase of adsorbed oxygen accelerates the reaction rate. With Cu/CeZrO 2 /γ-Al 2 O 3 Compared with Sn doping, ce on the surface of the catalyst is improved 3+ The content is as follows. The abundant oxygen vacancies help the adsorption of reactant gases, creating conditions for the oxidation reaction. Thus, the improvement of the oxygen vacancies of the catalystCan greatly improve the oxidation activity of CO and CH. 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 (182.4 eV) and Zr 3d 3/2 (184.7eV)。Zr 3d 5/2 Characteristic binding energy of 182.4eV, and ZrO 2 The binding energy of 182.4eV is consistent, indicating that Zr exists predominantly in the +4 oxidation state. From XPS spectrum of Sn 3d, cu/CeZrSnO 2 /γ-Al 2 O 3 Sn 3d in 5/2 The binding energy of the peak was 486.1eV, lower than the peak in tin oxide (486.2 eV), but higher than the peak of stannous oxide binding energy 485.6 eV. This means Sn 2+ /Sn 4+ Species co-existing in Cu/CeZrSnO 2 /γ-Al 2 O 3 Is a kind of medium.
As shown in FIG. 8 (b), the peak with the binding energy of Cu 3d XPS spectrum at 933.0-933.8eV is attributed to CuO (Cu) 2+ ) Cu2p of (2) 3/2 The method comprises the steps of carrying out a first treatment on the surface of the The peak with binding energy at 932.2-933.1eV is attributed to Cu 2 O(Cu 1+ ) Cu2p of (2) 3/2 . Description of Cu in the catalyst as CuO and Cu 2 O exists in both forms. The peak at 939.8-944.1eV is Cu 2+ The satellite peaks of (2) are believed to be generated by the final state effect of shell level vacancy shielded by valence electrons, and are found in Cu 2 O and elemental Cu were not observed. Calculating the area of the fitting peak, cu 2+ Relative content of (C) is Cu 2+ Peak area and Cu 1+ +Cu 2+ The ratio of peak areas. As a result, it can be seen that Cu in the Sn-doped catalyst 2+ The relative content of (2) is higher than that without Sn doping. This is because Cu and Ce are less electronegative than Sn, resulting in redox Cu 1+ +Sn 4+ →Cu 2+ +Sn 2+ Move to the right. This is in agreement with the results of the post quantum chemistry calculations. Cu (Cu) 2+ Is an active component with main catalytic effect, and the higher the relative content is, the more favorable the oxidation-reduction capability of the catalyst is improved.
To better understand the surface of the catalyst, the O1s XPS spectra are compared in fig. 8 (c). Wherein,the O1s peak is labeled as O (530.5 eV) O' (531.2 eV) O "(532.3 eV), O representing lattice oxygen; adsorbing oxygen on the surface of O'; o' is weak bond oxygen, such as molecular water or carbonate, etc. However, O 'is an important factor in oxidation reactions, particularly 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 ratio O '/(O "+o' +o). From the fitting results, it is known that in Cu/CeZrSnO 2 /γ-Al 2 O 3 The relative content of O' on the surface of the catalyst is higher than that of Cu/CeZrO 2 /γ-Al 2 O 3 High. Obviously, by doping Sn to CeZrO 2 In the crystal lattice, the oxidation activity of CO can be improved. This is in accordance with the following H 2 The results of the TPR are consistent.
FIG. 9 is a Cu/CeZrO 2 /γ-Al 2 O 3 With Cu/CeZrSnO 2 /γ-Al 2 O 3 H of the catalyst 2 -TPR profile. From the figure, it can be seen that there are four reduction peaks in both samples, the reduction peak at 300-400 ℃ being labeled α; the reduction peak at 450-550 ℃ is labeled as the beta peak; the reduction peak at 550-650 ℃ is marked as gamma peak; the reduction peak at 800-900 ℃ is labeled theta peak. Due to gamma-Al 2 O 3 CuO is easily dispersed into the carrier gamma-Al with high specific surface area 2 O 3 The alpha peak is attributed to the CuO species dispersed on the support surface. The beta peak at 465-480 ℃ is attributed to Cu species with strong interactions with the auxiliary, cu/CeZrO 2 /γ- Al 2 O 3 The beta peak of the catalyst is at 486 ℃, compared with Cu/CeZrSnO 2 /γ-Al 2 O 3 The beta peak of the catalyst was reduced to 467 ℃. The gamma peak at 550-650 ℃ is the surface 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 due to the doping of Sn, the surface Ce is improved 3+ Concentration to create more oxygen vacancies, ce 4+ The concentration decreases. The theta peak at 800-900 ℃ is attributed to the inner Ce layer 4+ And the reduction of bulk oxygen, compared with the sample without doped Sn, the surface and bulk reduction peaks of the doped Sn sample are moved to a low-temperature region, which shows that the doping of Sn improves the concentration of oxygen vacancies of the sample, and the more oxygen defects, the oxygen migrationThe faster the rate of movement, which in turn improves the catalyst catalytic performance, consistent with XPS results.
To further investigate 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 Catalyst is subjected to programmed temperature oxidation (O) 2 -TPD) analysis. FIG. 10 is a Cu/CeZrO 2 /γ-Al 2 O 3 With Cu/CeZrSnO 2 /γ-Al 2 O 3 O of (2) 2 -TPD profile. As can be seen from fig. 10, both samples consist of three peaks, the alpha peak at 100-200 ℃ is attributed to physically adsorbed oxygen species, which have weaker forces with the surface; adsorption O of beta peak and surface oxygen vacancy at 450-550 DEG C 2 The oxygen species formed are related and the gamma peak at 800-950 ℃ is related to desorption of lattice oxygen. As can be seen from fig. 10, the doping of Sn increases the beta peak desorption peak area compared to the undoped Sn sample, which suggests 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 lattice oxygen migration rate can provide the oxygen required for the oxidation reaction under the anoxic condition, thereby improving the catalytic performance of the catalyst. The increase in peak area of gamma peak desorption may be due to the synergistic effect between all redox couples, e.g. Ce 4+ /Ce 3+ And Sn (Sn) 4+ /Sn 2+ . The results show that there is a synergistic effect between the dopant Sn and the cerium zirconium solid solution, which is beneficial to improving the catalytic performance of the co-doped sample.
TG analysis was used to study the type and stability of sulfate on the catalyst surface 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 between 50 and 200 ℃, and mainly comprises the removal of physically adsorbed water on the surface of the catalyst and the dehydration of surface hydroxyl groups. The second stage is between 500 and 900 ℃, mainly the decomposition of sulfur species and the weight loss caused by partial structural collapse. Cu/CeZrO 2 /γ-Al 2 O 3 There is a distinct peak at 788℃due to CuSO 4 Is decomposed. But in Cu/CeZrSnO 2 /γ- Al 2 O 3 In the middle, no check is madeA 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, sn modification can reduce SO adsorbed on the surface of the active component 2 SO that SO 2 Is not easy to adsorb around Cu and inhibits the formation of sulfate on the active component. The formation of sulphates (e.g. ammonium sulphate and metal sulphates) is SO 2 The main cause of catalyst deactivation in the presence of the catalyst. 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 reducing SO 2 Has better catalytic activity in the presence.
Example 6
Similar to the preparation method of the three-way catalyst in the embodiment 1, the Cu/CeZrSnO is prepared under the conditions of optimal Cu loading and optimal active metal roasting temperature by using the same method 2 /γ-Al 2 O 3 The three-effect catalyst optimizes the reaction condition under the reactor and determines the optimal space velocity.
With Cu/CeZrSnO 2 /γ-Al 2 O 3 For the three-way catalyst, the catalytic activity is evaluated under different airspeed conditions in the reactor, and the temperature gradient is selected from 30000/h, 40000/h, 50000/h and 60000/h, so that the optimal airspeed is selected.
Placing 0.5mL of catalyst in a quartz tube, placing in a tube furnace, setting temperature programming, respectively obtaining final reaction temperatures of 600 ℃, introducing simulated atmosphere, 10000ppm CO,1000ppm NO,3000ppm CH (2000 ppm C) 3 H 8 +1000ppm C 3 H 6 )，0％～3％O 2 ，N 2 For balancing the gas, the flow rates of the mixed gas are 30000/h, 40000/h, 50000/h and 60000/h respectively, and timing is started at the same time; the concentration of CO, NO, CH in the outlet gas was measured with a flue gas analyzer every 20 minutes, and the removal rates of the three contaminants were calculated. The catalytic activity of the three-way catalyst takes the removal rate of CO, NO and CH as an evaluation index.
FIGS. 12 (a), (b) and (c) show Cu/CeZrSnO at different airspeeds, respectively 2 /γ-Al 2 O 3 Influence on CO, NO and CH removal effects. From the figure, the empty spaceSpeed pair Cu/CeZrSnO 2 /γ-Al 2 O 3 The catalytic activity of the catalyst is obviously influenced, and the influence on the removal efficiency of three pollutants basically accords with 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 pollutant, the smaller the space velocity, the larger the pollutant, the longer the effective contact time of the pollutant and the catalyst, the more thorough the catalytic conversion effect of the three-way catalyst on the pollutant, but the difference between the space velocity of 30000/h and 40000/h is not obvious, and the Cu/CeZrSnO is at 40000/h 2 /γ-Al 2 O 3 The removal rates of CO, NO and CH can reach 92%, 90% and 100%, so that the higher catalytic activity of the catalyst can be maintained, the overall treatment efficiency is not affected, and the cost is not increased, and therefore, the optimal airspeed is 40000/h.
Example 7
Similar to the preparation method of the three-way catalyst in the embodiment 1, the Cu/CeZrSnO is prepared under the conditions of optimal Cu loading and optimal active metal roasting temperature by using the same method 2 /γ-Al 2 O 3 The three-effect catalyst optimizes the reaction condition under the reactor and determines the optimal air-fuel ratio.
With Cu/CeZrSnO 2 /γ-Al 2 O 3 For the three-way catalyst, the catalytic activity was evaluated at different air-fuel ratios in the reactor, and the air-fuel ratio lambda was selected from 0.8, 0.9, 0.925, 0.95, 0.975, 1, 1.025, 1.05, 1.075, thereby screening the optimum air-fuel ratio.
Placing 0.5mL of catalyst in a quartz tube, placing in a tube furnace, setting temperature programming, adjusting air-fuel ratio to 0.8, 0.9, 0.925, 0.95, 0.975, 1, 1.025, 1.05, 1.075, introducing simulated atmosphere, 10000ppm CO,1000ppm NO,3000ppm CH (2000 ppm C) 3 H 8 +1000ppm C 3 H 6 )，0％～3％O 2 ，N 2 For balancing the gas, the flow rate of the mixed gas is 40000/h, and timing is started at the same time; the concentration of CO, NO, CH in the outlet gas was measured with a flue gas analyzer every 20 minutes, and the removal rates of the three contaminants were calculated. Catalytic activity of three-way catalyst for removing CO, NO and CHThe removal rate is an evaluation index.
FIGS. 13 (a) and (b) are Cu/CeZrO, respectively 2 /γ-Al 2 O 3 With Cu/CeZrSnO 2 /γ-Al 2 O 3 Is a schematic diagram of the oxygen concentration operation section. As can be seen from the figure, cu/CeZrSnO 2 /γ-Al 2 O 3 Is wider than Cu/CeZrO in air-fuel ratio operation region 2 /γ-Al 2 O 3 The catalyst has CO, NO and CH eliminating rate over 85% in the air-fuel ratio of 0.92-1.03.
Example 8
Similar to the preparation method of the three-way catalyst in the embodiment 1, the Cu/CeZrSnO is prepared under the conditions of optimal Cu loading and optimal active metal roasting temperature by using the same method 2 /γ-Al 2 O 3 And optimizing the reaction conditions of the three-way catalyst in the reactor, and determining the optimal reaction temperature.
With Cu/CeZrSnO 2 /γ-Al 2 O 3 The catalytic activity of the three-way catalyst is evaluated at different reaction temperatures in the 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 temperature programming, and introducing simulated atmosphere at final reaction temperatures of 200, 300, 400, 500, 600, 700 ℃ and 10000ppm CO,1000ppm NO,3000ppm CH (2000 ppm C) 3 H 8 +1000ppm C 3 H 6 )，0％～3％O 2 ，N 2 For balancing the gas, the flow rate of the mixed gas is 40000/h, and timing is started at the same time; the concentration of CO, NO, CH in the outlet gas was measured with a flue gas analyzer every 20 minutes, and the removal rates of the three contaminants were calculated. The catalytic activity of the three-way catalyst takes the removal rate of CO, NO and CH as an evaluation index.
FIGS. 14 (a), (b) and (c) show the difference in reaction temperature versus Cu/CeZrSnO, respectively 2 /γ-Al 2 O 3 Influence on CO, NO and CH removal effects. As can be seen from the graph, the temperature is relative to Cu/CeZrSnO 2 /γ-Al 2 O 3 The catalytic performance of the catalyst has obvious effectThe method is sound, and the rules of the removal efficiency of three pollutants basically accord with the following rules: the catalytic performance increases with increasing temperature. The catalyst has the best catalytic activity at 600 ℃ and 700 ℃ when the catalytic performance of the catalyst reaches more than 90%. While ensuring effective removal of pollutants, energy consumption is saved, 600 ℃ is selected as the optimal reaction temperature, so that the catalytic performance of the catalyst can be maintained, and the cost is not increased.
Although a few embodiments of the present general inventive concept have been shown and described, it would 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 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, the CeZrSnO 2 The auxiliary agent enters the gamma-Al through an impregnation mode 2 O 3 In a carrier to form CeZrSnO 2 /γ-Al 2 O 3 A complex; and
active metal copper which enters the CeZrSnO in a dipping mode 2 /γ-Al 2 O 3 In the complex;
sn in CeZrSnO 2 The mole number of the auxiliary agent is 5-30%,
the molar ratio of Ce to Zr is 3:1, a step of;
the mass ratio of copper in the three-way catalyst is 5wt percent to 10wt percent,
the gamma-Al 2 O 3 Carrier and CeZrSnO 2 The mass ratio of the auxiliary agent is 25 (2-8).
2. A method of preparing the three-way catalyst of claim 1, 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 the carrier and the first mixed solution to form a second mixed solution, adding ammonia water solution into the second mixed solution to carry out impregnation 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 compound is mixed with a copper source solution to be carried out water bath dipping load to obtain a second reactant, and the second reactant is roasted to obtain Cu/CeZrSnO 2 /γ-Al 2 O 3 Is a three-way catalyst.
3. The preparation method according to claim 2, wherein,
Cu/CeZrSnO 2 /γ-Al 2 O 3 the three-way catalyst is prepared by a two-step impregnation method.
4. The preparation method according to claim 2, wherein,
the cerium source comprises at least one of cerium nitrate and hydrate thereof, cerium chloride and hydrate thereof, ammonium cerium nitrate and hydrate thereof, ammonium cerium sulfate and hydrate thereof;
the zirconium source comprises at least one of zirconium chloride and hydrate thereof, zirconyl nitrate and hydrate thereof, zirconium acetate and hydrate 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 its hydrate, copper chloride and its hydrate.
5. The preparation method according to claim 3, wherein,
the cerium source comprises at least one of cerium nitrate and hydrate thereof, cerium chloride and hydrate thereof, ammonium cerium nitrate and hydrate thereof, ammonium cerium sulfate and hydrate thereof;
the zirconium source comprises at least one of zirconium chloride and hydrate thereof, zirconyl nitrate and hydrate thereof, zirconium acetate and hydrate 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 its hydrate, copper chloride and its hydrate.
6. The preparation method according to claim 4, wherein,
in providing gamma-Al 2 O 3 In the process of the carrier, the pseudo-boehmite powder is calcined at 700-900 ℃ for 3-5 hours.
7. The preparation method according to claim 5, wherein,
in providing gamma-Al 2 O 3 In the process of the carrier, the pseudo-boehmite powder is calcined at 700-900 ℃ for 3-5 hours.
8. The preparation method according to claim 6 or 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 105-120 ℃ for 10-15 hours, and then roasted at 600-800 ℃ for 2-5 hours.
9. The preparation method according to claim 8, wherein,
during the process of obtaining the second reactant, ceZrSnO 2 /γ-Al 2 O 3 The compound is mixed with the copper source solution and then is carried out water bath dipping load, the temperature is 50-80 ℃ and the time is 0.5-3 hours;
in the process of roasting the second reactant, the second reactant is dried at 105-120 ℃ for 10-15 hours, and then roasted at 600-800 ℃ for 1-3 hours.
10. Three-way catalyst for removing CO, NO and C in automobile exhaust x H y The three-way catalyst is the three-way catalyst according to claim 1 or the three-way catalyst prepared by the preparation method according to any one of claims 4 to 9,
wherein the three-way catalyst is used for removing CO, NO and C in automobile exhaust at an airspeed of 30000/h-60000/h, an air-fuel ratio of 0.8-1.075 and a reaction temperature of 500-800 DEG C x H y 。
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