CN110694621A - 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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- CN110694621A CN110694621A CN201910848963.XA CN201910848963A CN110694621A CN 110694621 A CN110694621 A CN 110694621A CN 201910848963 A CN201910848963 A CN 201910848963A CN 110694621 A CN110694621 A CN 110694621A
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- cerium
- zirconium
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- composite alumina
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims abstract description 101
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000002131 composite material Substances 0.000 claims abstract description 56
- 239000006104 solid solution Substances 0.000 claims abstract description 48
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims abstract description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 3
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 3
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 3
- 239000010948 rhodium Substances 0.000 claims abstract description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 16
- 229910052684 Cerium Inorganic materials 0.000 claims description 12
- 229910052726 zirconium Inorganic materials 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 10
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 9
- -1 cerium ions Chemical class 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000012716 precipitator Substances 0.000 claims description 6
- 229910002637 Pr6O11 Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 20
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- 238000003860 storage Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 23
- 229910002091 carbon monoxide Inorganic materials 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000002002 slurry Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 6
- 238000010335 hydrothermal treatment Methods 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000005639 Lauric acid Substances 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000003916 acid precipitation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 2
- JUBNUQXDQDMSKL-UHFFFAOYSA-N palladium(2+);dinitrate;dihydrate Chemical compound O.O.[Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JUBNUQXDQDMSKL-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- WPQBNJRIWONKBL-UHFFFAOYSA-N cerium(3+);oxygen(2-);zirconium(4+) Chemical class [O-2].[Zr+4].[Ce+3] WPQBNJRIWONKBL-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical group [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100001143 noxa Toxicity 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009323 psychological health Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B01J35/613—
-
- B01J35/615—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Abstract
The application discloses a three-way catalyst, a preparation method and application thereof, and belongs to the field of adsorption catalyst materials. The three-way catalyst for CO oxidation reaction comprises cerium-zirconium composite alumina loaded with noble metal, wherein the noble metal content in the three-way catalyst is 0.5-1.5 wt%, and the cerium-zirconium composite alumina comprises cerium-zirconium solid solution and gamma-Al2O3gamma-Al in the cerium-zirconium composite alumina2O3The content of (A) is 20 wt% -50 wt%, and the cerium-zirconium solid solution comprises 20 wt% -50 wt% of CeO2And 38 wt% to 65 wt% ZrO2(ii) a The noble metal is at least one selected from the group consisting of platinum, rhodium and palladium. The three-way catalyst has the advantages of low temperature, large oxygen storage amount, excellent ageing resistance and good high-temperature stability in CO catalytic oxidation.
Description
Technical Field
The application relates to a three-way catalyst and a preparation method and application thereof, belonging to the field of adsorption catalyst materials.
Background
With the continuous and rapid prosperity of the economic society of China, the automobile conservation quantity rises linearly. The rapid development of motor vehicles is also accompanied by severe atmospheric pollution. Therefore, the work of controlling the automobile exhaust emission pollution becomes very difficult, especially in big cities, the situation is more severe, and about 60-80% of the total amount of the atmospheric pollutants come from the automobile exhaust emission. The automobile exhaust contains hundreds of different compounds, and the pollutants mainly comprise carbon monoxide (CO) and Nitrogen Oxide (NO)x) Hydrocarbon (HC), suspended solid particles, sulfur oxides, and the like. Wherein CO is colorless and odorless, is a suffocating toxic gas, and can be combined with hemoglobin (Hb) at a very rapid speed, compared with O2The bonding speed of (a) is 250 times faster. Meanwhile, under the condition of high temperature, nitrogen and oxygen in the air of the engine are subjected to chemical reaction to generate NOxA contaminant. The pollutants cause serious damage and harm to the environment and human health, for example, high concentration of NO may cause mild central nervous disorder, NO may damage high altitude ozone protective layer, nitrogen dioxide can combine with water vapor in atmosphere to cause acid rain, NO2Is also the main reason for generating acid rain, climate change and smog, NO2When the catalyst is used together with HC, photochemical reaction can be generated to form photochemical smog, which directly threatens the physical and psychological health of people.
At present, the problem of controlling the emission pollution of the motor vehicle is mainly solved by a Three-way catalytic converter (TWC) pollution control device, so that increasingly strict emission standards put higher requirements on the industry of the Three-way catalyst.
The three-way catalyst mainly comprises a carrier, a coating, an active component and an auxiliary agent. For example, the support is a cordierite ceramic support and the active component can be both noble and non-noble types. The noble metal has a low melting point, and is easy to aggregate, grow and run off at high temperature, so that the catalytic activity is greatly reduced and even inactivated, the high-temperature stability of the noble metal catalyst is improved, and the ignition temperature of polluted gases such as CO is reduced, which becomes a problem to be solved urgently. In addition, the lower pollutant emission limits of the light motor vehicles of state six require high conversion efficiency and long service life of the catalyst.
Disclosure of Invention
In order to solve the problems, the three-way catalyst for catalyzing CO oxidation is low in temperature and stable in high temperature, and the preparation method and the application of the three-way catalyst are provided.
According to one aspect of the application, a three-way catalyst for catalyzing CO oxidation is provided, and comprises cerium-zirconium composite alumina loaded with noble metal, wherein the noble metal content of the three-way catalyst is 0.5 wt% -1.5 wt%, and the cerium-zirconium composite alumina comprises cerium-zirconium solid solution and gamma-Al2O3gamma-Al in the cerium-zirconium composite alumina2O3The content of (A) is 20-50 wt%, and the cerium-zirconium solid solution comprises 20-50 wt% of CeO2And 38-65 wt% ZrO2(ii) a The noble metal is at least one selected from the group consisting of platinum, rhodium and palladium.
Optionally, the three-way catalyst has a noble metal content of 1 wt%.
Preferably, the noble metal is palladium.
Optionally, gamma-Al in the cerium zirconium composite alumina2O3The content of (B) is 30-50 wt%.
Optionally, the cerium zirconium solid solution further comprises 2 wt% -4 wt% of La2O3And 10 wt% to 15 wt% Y2O3. Preferably, the cerium zirconium solid solution further comprises 3 wt% of La2O3And 12.5 wt% Y2O3。
Optionally, the cerium zirconium solid solution further comprises 4 wt% -7 wt% of La2O3And 4 wt% -8 wt% of Pr6O11. Preferably, the cerium zirconium solid solution further comprises 5.5% La2O3And 6 wt% of Pr6O11。
According to another aspect of the present application, there is provided a method for preparing the three-way catalyst, comprising the steps of:
1) providing a cerium zirconium solid solution;
2) mixing cerium-zirconium solid solution with gamma-Al2O3Mixing, and carrying out first roasting to obtain cerium-zirconium composite alumina;
3) and loading the noble metal on the cerium-zirconium composite alumina by an isometric impregnation method, and performing second calcination to obtain the three-way catalyst.
Optionally, the preparation method of the cerium zirconium solid solution of step 1) includes:
A. mixing materials: preparing raw materials into a primary mixture of a strong metal acid aqueous solution at least containing cerium ions and zirconium ions;
B. a first hydrothermal reaction: adding an alkaline precipitator into the primary mixture to prepare an acid mixture with the pH value of 1.5-2.0, and carrying out a first hydrothermal reaction on the acid mixture to prepare a precursor solution;
C. a second hydrothermal reaction: adding an alkaline precipitator into the precursor solution to prepare an alkaline mixture with the pH value of 8-11, and carrying out second hydrothermal reaction, filtering, washing and first calcining to obtain the cerium-zirconium composite oxide.
Optionally, the temperature of the first hydrothermal reaction is 160-200 ℃ and the time is 15-25 h.
Optionally, the temperature of the second hydrothermal reaction is 160-200 ℃ and the time is 6-10 h.
Optionally, the first calcining comprises: heating to 250-300 ℃ at the rate of 40-60 ℃/h and keeping for 3-5h, and heating to 700-800 ℃ at the rate of 110-130 ℃/h and keeping for 3-5 h.
Optionally, the oxide concentration of the metal in the initial mixture is 85-160 g/L. Preferably, the oxide concentration of the metal in the initial mixture is 110-140 g/L.
Optionally, the cerium zirconium solid solution in the step 2) is mixed with gamma-Al2O3The mixing comprises the following steps: the gamma-Al is added2O3Ball-milling for 8-12h under the protection of inert gas with the ball-material ratio of 8: 1 and the rotating speed of 250r/min, adding the cerium-zirconium solid solution, and continuing ball-milling for 5-25 h. Traditional mechanical mixing has easy operation, labour saving and time saving's advantage, but the homogeneity of mixing is poor, and the mixing method of this application can improve the homogeneity of mixing.
Optionally, the first firing comprises: roasting at 800-900 deg.c for 1-5 hr.
As an embodiment, the cerium-zirconium solid solution in the step 2) is mixed with γ -Al2O3The method of mixing comprises the steps of: according to the composite proportion of cerium, zirconium and alumina, firstly adding a certain amount of gamma-Al2O3Ball milling is carried out for 10 hours under the conditions that the ball material ratio is 8: 1, the rotating speed is 250r/min and nitrogen is used as protective gas, the particle size distribution is uniform, then cerium and zirconium with corresponding amount are added for ball milling for 20 hours, the cerium and zirconium are fully mixed, and finally, the cerium and zirconium composite alumina sample is prepared by roasting at 850 ℃ for 3 hours.
As an embodiment, the step 3) is performed by using palladium nitrate dihydrate (Pd (NO)3)2·2H2O) is a noble metal precursor, and the isovolumetric impregnation method for preparing a sample with a theoretical loading of noble metal Pd of 1 wt% comprises the following steps:
0.13g Pd (NO) was weighed3)2·2H2Dissolving O in 11.5mL of deionized water, dropwise adding a palladium nitrate aqueous solution into 5g of the cerium-zirconium composite alumina carrier, drying the catalyst slurry loaded with the Pd metal in a rotary evaporator, then placing the catalyst slurry in a forced air drying oven at 110 ℃ for drying for 3 hours, and then placing the catalyst slurry in a calcining furnace to calcine for 3 hours at 500 ℃ in a nitrogen atmosphere.
Optionally, the second calcination is calcination at 450-550 ℃ for 2-6 h. Preferably, the second calcination is calcination at 500 ℃ for 3 h.
According to a further aspect of the present application there is provided the use of a three-way catalyst selected from any of the three-way catalysts described above in a CO oxidation reaction.
Benefits of the present application include, but are not limited to:
1. the three-way catalyst for catalyzing CO oxidation has the excellent performances of low temperature, large oxygen storage amount, high ageing resistance and high temperature stability for catalyzing CO oxidation.
2. The preparation method of the three-way catalyst has the advantages of simple preparation method, low cost and easy industrialization.
3. According to the application of the three-way catalyst in catalyzing CO oxidation, the three-way catalyst can realize low-temperature high conversion rate of CO when being used for catalyzing CO oxidation.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and solvents in the examples of the present application were all purchased commercially. Gamma-alumina with a purity of > 99.0% was purchased from Zibozifeng aluminum industries, Inc.
The analysis method in the examples of the present application is as follows:
analysis of the specific surface area of the three-way catalyst was carried out using a Micromeritics TriStar model II fully automated adsorption apparatus from Mac instruments USA.
The analysis of the oxygen storage capacity of the three-way catalyst was carried out using the ChemBET-3000 instrument from Kangta.
Analysis of the three-way catalyst reduction temperature was performed using a PCA1200-TPR instrument from Pioder.
The method for evaluating the conversion rate of CO catalytically oxidized by the three-way catalyst comprises the following steps:
1) the activity evaluation of the catalyst is carried out on a self-made small sample evaluation reaction device provided with a U-shaped quartz reaction tube, a small group of quartz wool is plugged at the bottom of one side of the U-shaped quartz reaction tube, a weighed catalyst sample is placed, and mixed gas is introduced for determination;
2) the reaction is carried out at normal pressure, the loading of the catalyst is 120mg, the granularity is 40-60 meshes, and the volume of the raw material gas comprises: 3.76% CO, 6.24％O2、90％N2Space velocity 25000mL g-1·h-1The reaction temperature rise rate is 2 ℃/min;
3) the composition of the gas after passing through the catalyst was detected by chromatography, and the conversion of CO was calculated from the change in gas content before and after analysis.
According to one embodiment of the present application, a method of preparing a three-way catalyst comprises the steps of:
1) providing a cerium zirconium solid solution;
a, mixing materials: preparing raw materials into a primary mixture of a strong acid aqueous solution of rare earth metal at least containing cerium ions and zirconium ions, wherein the oxide concentration of the metal in the primary mixture is 85-160 g/L;
b, first hydrothermal reaction: adding an alkaline precipitator into the primary mixture to prepare an acid mixture with the pH value of 1.5-2.0, and carrying out a first hydrothermal reaction on the acid mixture to prepare a precursor solution; the temperature of the first hydrothermal reaction is 160-200 ℃ and the time is 15-25 h;
c, second hydrothermal reaction: adding an alkaline precipitator into the precursor solution to prepare an alkaline mixture with the pH value of 8-11, and carrying out second hydrothermal reaction, filtering, washing and first calcining to prepare the cerium-zirconium composite oxide; the temperature of the second hydrothermal reaction is 160-200 ℃ and the time is 6-10 h; the first calcination includes: heating to 250-300 ℃ at the rate of 40-60 ℃/h and keeping for 3-5h, heating to 700-800 ℃ at the rate of 110-130 ℃/h and keeping for 3-5 h;
2) mixing cerium-zirconium solid solution with gamma-Al2O3Mixing, and carrying out first roasting to obtain cerium-zirconium composite alumina;
cerium zirconium solid solution and gamma-Al2O3The mixing comprises the following steps: subjecting the gamma-Al to2O3Ball-milling for 8-12h under the protection of inert gas with the ball-material ratio of 8: 1 and the rotating speed of 250r/min, adding the cerium-zirconium solid solution, and continuing ball-milling for 5-25 h; the first firing includes: roasting at 800-900 deg.c for 1-5 hr;
3) loading noble metal on the cerium-zirconium composite alumina by an isometric impregnation method, and performing second calcination to prepare a three-way catalyst;
the second calcination was at 500 ℃ for 3 h.
EXAMPLE 1 preparation of cerium-zirconium solid solution CZ1#
The composition of the cerium-zirconium solid solution CZ1# comprises 22% of CeO2、62.5％ZrO2、3％La2O3And 12.5% Y2O3. The concentration of the metal oxide in the primary mixture is 120g/L, the reaction kettle is a 10L titanium kettle, and the total mass of the oxide is 725 g.
Weighing 1435.3g of zirconium nitrate, and dissolving with 2500mL of deionized water until the solution is clear; 90.6g of yttrium oxide is weighed out, dissolved by 191.5g of concentrated nitric acid until the solution is clear, and the two solutions are combined to obtain solution A. 495.8g of ammonium ceric nitrate and 56.8g of lanthanum nitrate are weighed out and added to the solution A, and stirred until the solution is clear. Then, the pH of the solution A is adjusted to 1.5-2.0 by using ammonia water under the condition of 50 ℃ water bath, and finally, the solution is metered to 7500 mL. And introducing the solution A into a pressure soluble bomb of a polytetrafluoroethylene lining, and carrying out hydrothermal hydrolysis at 180 ℃ for 20 h. And (3) adjusting the pH of the slurry obtained after the hydrothermal reaction to about 9.5 by using ammonia water at normal temperature to obtain slurry B. Transferring the slurry B into a 10L titanium kettle, and carrying out hydrothermal treatment at 180 ℃ for 8h under the condition of the rotating speed of 25 HZ. The slurry after hydrothermal treatment was press-filtered, washed 3 times with 50L of deionized water, 2 times with 560g of lauric acid solution, and the organic matter obtained by suction filtration was recovered. Calcining the washed filter cake at high temperature for removing rubber, wherein the calcining conditions are as follows: raising the temperature at 270 ℃ for 5h, preserving the heat at 750 ℃ for 4h, and preserving the heat for 4 h; the flow rate of the furnace body gas is controlled at 10-20L (air)/min/kg (oxide). Sieving the calcined material with a 200-sand 250-mesh sieve to obtain the final product of the cerium-zirconium solid solution CZ1 #.
EXAMPLE 2 preparation of cerium-zirconium solid solution CZ2#
The composition of the cerium-zirconium solid solution CZ2# is 49 percent of CeO2、39.5％ZrO2、6％Pr6O11And 5.5% La2O3. The concentration of the metal oxide in the primary mixture is 120g/L, the reaction kettle is a 10L titanium kettle, and the total mass of the oxide is 840 g.
Weighing 1050.9g of zirconium nitrate, and dissolving with 2500mL of deionized water until the solution is clear; 50.4g of praseodymium oxide is weighed out and dissolved by 100.8g of concentrated nitric acid until the solution is clear, and the two solutions are combined to obtain solution A. 1279.5g of ammonium ceric nitrate and 120.6g of lanthanum nitrate are weighed and added into the solution A, and the mixture is stirred until the solution is clear. Then, the pH of the solution A is adjusted to 1.5-2.0 by using ammonia water under the condition of 50 ℃ water bath, and finally, the solution is metered to 7500 mL. And introducing the solution A into a pressure soluble bomb of a polytetrafluoroethylene lining, and carrying out hydrothermal hydrolysis at 180 ℃ for 20 h. And (3) adjusting the pH of the slurry obtained after the hydrothermal reaction to about 9.5 by using ammonia water at normal temperature to obtain slurry B. Transferring the slurry B into a 10L titanium kettle, and carrying out hydrothermal treatment at 180 ℃ for 8h under the condition of the rotating speed of 25 HZ. The slurry after hydrothermal treatment was press-filtered, washed 3 times with 50L of deionized water, 2 times with 560g of lauric acid solution, and the organic matter obtained by suction filtration was recovered. Calcining the washed filter cake at high temperature for removing rubber, wherein the calcining conditions are as follows: raising the temperature at 270 ℃ for 5h and preserving the heat for 4h, and raising the temperature at 750 ℃ for 4h and preserving the heat for 4 h; the flow rate of the furnace body gas is controlled at 10-20L (air)/min/kg (oxide). Sieving the calcined material with a 200-sand 250-mesh sieve to obtain the final product of the cerium-zirconium solid solution CZ2 #.
EXAMPLE 3 preparation of cerium-zirconium solid solution CZ3#
The composition of the cerium-zirconium solid solution CZ3# is 35 percent of CeO2、58％ZrO2、4％Pr6O11、3％Y2O3. The concentration of the metal oxide in the primary mixture is 120g/L, the reaction kettle is a 10L titanium kettle, and the total mass of the oxide is 800 g.
1469.7g of zirconium nitrate is weighed and dissolved in 3000mL of deionized water until the solution is clear, so that solution A is obtained. 24.1g of yttrium oxide is weighed and dissolved by 56.6g of concentrated nitric acid until the solution is clear, 32.6g of praseodymium oxide is dissolved by 67.8g of concentrated nitric acid until the solution is clear, and 3 solutions are combined to obtain solution A. 870.4g of ammonium ceric nitrate was weighed out and added to the solution A, and stirred until it was clear. Then, the pH of the solution A is adjusted to 1.5-2.0 by using ammonia water under the condition of 50 ℃ water bath, and finally, the solution is metered to 7500 mL. And introducing the solution A into a pressure soluble bomb of a polytetrafluoroethylene lining, and carrying out hydrothermal hydrolysis at 180 ℃ for 20 h. And (3) adjusting the pH of the slurry obtained after the hydrothermal reaction to about 9.5 by using ammonia water at normal temperature to obtain slurry B. Transferring the slurry B into a 10L titanium kettle, and carrying out hydrothermal treatment at 180 ℃ for 8h under the condition of the rotating speed of 25 HZ. The slurry after hydrothermal treatment was press-filtered, washed 3 times with 50L of deionized water, 2 times with 560g of lauric acid solution, and the organic matter obtained by suction filtration was recovered. Calcining the washed filter cake at high temperature for removing rubber, wherein the calcining conditions are as follows: raising the temperature at 270 ℃ for 5h and preserving the heat for 4h, and raising the temperature at 750 ℃ for 4h and preserving the heat for 4 h; the flow rate of the furnace body gas is controlled at 10-20L (air)/min/kg (oxide). Sieving the calcined material with a 200-sand 250-mesh sieve to obtain the final product of the cerium-zirconium solid solution CZ3 #.
EXAMPLE 4 preparation of cerium zirconium composite alumina CZ1-A1# -3#
Mechanically mixing cerium-zirconium solid solution CZ1# with gamma-alumina to obtain cerium-zirconium composite alumina CZ1-A1#, CZ1-A2#, and CZ1-A3#, wherein the gamma-alumina contents are 20 wt%, 50 wt% and 30 wt%, respectively. Ce in the sample3+、Zr4+Mixed on an atomic scale, Ce3+、Zr4+And Al3+Interact on a powder scale.
The step of mechanically mixing comprises: according to the composite proportion of cerium, zirconium and alumina, firstly adding a certain amount of gamma-Al2O3Ball milling is carried out for 10 hours under the conditions that the ball material ratio is 8: 1, the rotating speed is 250r/min and nitrogen is used as protective gas, the particle size distribution is uniform, then cerium and zirconium with corresponding amount are added for ball milling for 20 hours, the cerium and zirconium are fully mixed, and finally, the cerium and zirconium composite alumina sample is prepared by roasting at 850 ℃ for 3 hours. A planetary high-energy ball mill Pulverisette 4 is adopted, a stainless steel tank and quenching steel balls are used, and a box type resistance furnace SX-5-12 is adopted for powder roasting.
Example 5 preparation of cerium zirconium composite alumina CZ2-A1# -3#, CZ3-A1# -3#
According to the preparation method of the cerium-zirconium composite alumina CZ1-A1# of the embodiment 4, the cerium-zirconium composite alumina CZ2-A1# -3# and CZ3-A1# -3# are respectively prepared, which is different from the preparation method of the cerium-zirconium composite alumina CZ1-A1 #:
mechanically mixing cerium-zirconium solid solution CZ2# with gamma-alumina to obtain cerium-zirconium composite alumina CZ2-A1#, CZ2-A2#, and CZ2-A3#, wherein the gamma-alumina contents are 20 wt%, 50 wt% and 30 wt%, respectively.
Mechanically mixing cerium-zirconium solid solution CZ3# with gamma-alumina to obtain cerium-zirconium composite alumina CZ3-A1#, CZ3-A2#, and CZ3-A3#, wherein the gamma-alumina contents are 20 wt%, 50 wt% and 30 wt%, respectively.
Example 6 preparation of three-way catalyst CZ1-A-Pd1# -3#, CZ2-A-Pd1# -3# and CZ3-A-Pd1# -3#
The prepared cerium-zirconium composite alumina CZ1-A1# to 3#, CZ2-A1# to 3# and CZ3-A1# respectively load 1 wt% of Pd to prepare three-way catalysts CZ1-A-Pd1# to 3#, CZ2-A-Pd1# to 3# and CZ3-A-Pd1# to 3 #.
The method for preparing the three-way catalyst CZ1-A-Pd1# by taking the cerium-zirconium composite alumina CZ1-A1# loaded with 1 wt% of Pd as an example illustrates that the method for loading the cerium-zirconium composite alumina with Pd comprises the following steps: with palladium nitrate dihydrate (Pd (NO)3)2·2H2O) is a noble metal precursor. A sample was prepared with a theoretical loading of noble metal Pd of 1 wt%.
Comparative example 1 preparation of comparative cerium-zirconium composite alumina CZ1-DA1#
The preparation method of the cerium zirconium composite alumina CZ1-A1# of example 4 is used for preparing CZ1-DA1#, which is different from the preparation method of the cerium zirconium composite alumina CZ1-A1 #: mechanically mixing the cerium-zirconium solid solution CZ1# with gamma-alumina to obtain a comparative cerium-zirconium composite alumina CZ1-DA1# with the gamma-alumina content of 80 wt%.
Comparative example 2 preparation of comparative cerium-zirconium composite alumina CZ2-DA1#, CZ3-DA1#, and
the preparation method of the cerium zirconium composite alumina CZ2-A1# in example 5 is used for preparing CZ2-DA1#, which is different from the preparation method of the cerium zirconium composite alumina CZ1-A1 #: mechanically mixing the cerium-zirconium solid solution CZ2# with gamma-alumina to obtain the comparative cerium-zirconium composite alumina CZ2-DA1# with the gamma-alumina content of 80 wt%.
According to the preparation method of the cerium-zirconium composite alumina CZ3-A1# in example 5, CZ3-DA1# is prepared, which is different from the preparation method of the cerium-zirconium composite alumina CZ3-A1 #: mechanically mixing the cerium-zirconium solid solution CZ3# with gamma-alumina to obtain the comparative cerium-zirconium composite alumina CZ3-DA1# with the gamma-alumina content of 80 wt%.
Comparative example 3 preparation of comparative three-way catalysts CZ1-DA-Pd1#, CZ2-DA-Pd1#, CZ3-DA-Pd1#, and CZD1# -Pd
According to the method of the embodiment 6, 1 wt% of Pd is loaded on the prepared comparative cerium-zirconium composite alumina CZ1-DA1#, CZ2-DA1#, CZ3-DA1# and the cerium-zirconium solid solution CZ1#, so that comparative three-way catalysts CZ1-A-Pd1# -3#, CZ2-A-Pd 1-3 #, CZ3-A-Pd1# 3# and CZD1# -Pd are prepared.
Example 7 Performance tests of the cerium-zirconium solid solution CZ1# -3#, the cerium-zirconium composite alumina CZ1-A1# -3#, the cerium-zirconium composite alumina CZ2-A1# -3#, and the cerium-zirconium composite alumina CZ3-A1# -3#
The results of testing the surface area and oxygen storage capacity of the cerium-zirconium solid solution CZ1# -3#, the cerium-zirconium composite alumina CZ1-A1# -3#, the cerium-zirconium composite alumina CZ2-A1# -3#, and the cerium-zirconium composite alumina CZ3-A1# -3# after being calcined at 750 ℃ for 4 hours, and the surface area and oxygen storage capacity after being aged at 1100 ℃ for 4 hours are shown in Table 1.
TABLE 1
The cerium-zirconium composite alumina prepared by the embodiment of the application has larger surface area and oxygen storage amount than cerium-zirconium solid solution. The surface area and oxygen storage capacity after 1100 ℃ aging show that the cerium-zirconium composite alumina prepared by the embodiment of the application has good aging resistance and high thermal stability.
Example 8 conversion test of three-way catalyst for catalytic Oxidation of CO
Carrying out catalytic oxidation CO reaction performance tests on three-way catalysts CZ1-A-Pd1# -3#, CZ2-A-Pd1# -3#, CZ3-A-Pd1# -3# and comparative three-way catalysts CZ1-DA-Pd1#, CZ2-DA-Pd1#, CZ3-DA-Pd1# and CZD1# -Pd; and the results of verifying the catalytic CO oxidation reaction performance after aging at high temperatures of 1100 c for 4 hours, respectively, are shown in table 2. T50 in Table 2 refers to the temperature at which 50% of CO is converted and T90 refers to the temperature at which 90% of CO is converted.
TABLE 2
| Product type | T50/℃ | T90/℃ |
| CZ1-A-Pd1# | 95 | 120 |
| CZ1-A-Pd2# | 87 | 124 |
| CZ1-A-Pd3# | 85 | 116 |
| CZ1-DA-Pd1# | 110 | 138 |
| CZ1-A-Pd1# aging | 102 | 135 |
| CZ1-A-Pd2# aging | 98 | 119 |
| CZ1-A-Pd3# aging | 93 | 112 |
| Aging with CZ1-DA-Pd1# | 118 | 147 |
| CZ2-A-Pd1# | 89 | 123 |
| CZ2-A-Pd2# | 82 | 116 |
| CZ2-A-Pd3# | 78 | 110 |
| CZ2-DA-Pd1# | 103 | 132 |
| CZ2-A-Pd1# aging | 96 | 125 |
| CZ2-A-Pd2# aging | 88 | 115 |
| CZ2-A-Pd3# aging | 83 | 108 |
| Aging with CZ2-DA-Pd1# | 112 | 141 |
| CZ3-A-Pd1# | 92 | 121 |
| CZ3-A-Pd2# | 85 | 118 |
| CZ3-A-Pd3# | 81 | 113 |
| CZ3-DA-Pd1# | 106 | 135 |
| CZ3-A-Pd1# aging | 102 | 137 |
| CZ3-A-Pd2# aging | 95 | 128 |
| CZ3-A-Pd3# aging | 91 | 124 |
| Aging with CZ3-DA-Pd1# | 115 | 143 |
| CZD1#-Pd | 101 | 130 |
| CZD1# -Pd aging | 119 | 151 |
From the results in table 2, it can be seen that, when the composite catalyst is prepared with three cerium-zirconium oxides with different component contents according to the alumina contents of 20%, 30%, 50% and 80%, the alumina contents of 20-50 wt% all show better CO oxidation activity, wherein the catalytic effect is the best when the alumina content is 30%, and the catalytic effect is obviously reduced when the alumina content is 80 wt%. Compared with the sample CZD1# -Pd before and after aging, the introduction of the proper amount of alumina improves the oxygen storage performance and the aging resistance of cerium zirconium, thereby improving the thermal stability and the catalytic activity of the cerium zirconium for catalyzing CO reaction. The three-way catalyst in the embodiment has the excellent performances of high low-temperature conversion rate of CO catalytic oxidation, high-temperature stability and high performance.
The above description is only an example of the present application, and the protection scope of the present application is not limited by these specific examples, but is defined by the claims of the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The three-way catalyst for catalyzing CO oxidation is characterized by comprising cerium-zirconium composite alumina loaded with noble metal, wherein the noble metal content in the three-way catalyst is 0.5-1.5 wt%, and the cerium-zirconium composite alumina comprises cerium-zirconium solid solution and gamma-Al2O3gamma-Al in the cerium-zirconium composite alumina2O3The content of (A) is 20 wt% -50 wt%, and the cerium-zirconium solid solution comprises 20 wt% -50 wt% of CeO2And 38 wt%
-65wt％ZrO2(ii) a The noble metal is at least one selected from the group consisting of platinum, rhodium and palladium.
2. The three-way catalyst according to claim 1, wherein the noble metal content of the three-way catalyst is 1 wt.%;
preferably, the noble metal is palladium.
3. The three-way catalyst according to claim 1, wherein γ -Al in the cerium zirconium composite alumina2O3The content of (B) is 30-40 wt%.
4. The three-way catalyst according to claim 1, wherein the cerium zirconium solid solution further comprises 2-4 wt% La2O3And 10 wt% to 15 wt% Y2O3；
Preferably, the cerium and zirconium are solid solutionThe body also comprises 3 wt% La2O3And 12.5 wt% Y2O3。
5. The three-way catalyst according to claim 1, wherein the cerium zirconium solid solution further comprises 4 wt% to 7 wt% La2O3And 4 wt% -8 wt% of Pr6O11；
Preferably, the cerium zirconium solid solution further comprises 5.5% La2O3And 6 wt% of Pr6O11。
6. Process for the preparation of a three-way catalyst according to any one of claims 1 to 5, characterized in that it comprises the following steps:
1) providing a cerium zirconium solid solution;
2) mixing cerium-zirconium solid solution with gamma-Al2O3Mixing, and carrying out first roasting to obtain cerium-zirconium composite alumina;
3) and loading the noble metal on the cerium-zirconium composite alumina by an isometric impregnation method, and performing second calcination to obtain the three-way catalyst.
7. The method according to claim 6, wherein the method of preparing the cerium-zirconium solid solution of step 1) comprises:
A. mixing materials: preparing a raw material into a primary mixture of a strong acid aqueous solution of a metal containing at least cerium ions and zirconium ions;
B. a first hydrothermal reaction: adding an alkaline precipitator into the primary mixture to prepare an acid mixture with the pH value of 1.5-2.0, and carrying out a first hydrothermal reaction on the acid mixture to prepare a precursor solution;
C. a second hydrothermal reaction: adding an alkaline precipitator into the precursor solution to prepare an alkaline mixture with the pH value of 8-11, and carrying out second hydrothermal reaction, filtering, washing and first calcining to prepare the cerium-zirconium solid solution;
wherein the temperature of the first hydrothermal reaction is 160-200 ℃ and the time is 15-25 h;
the temperature of the second hydrothermal reaction is 160-200 ℃, and the time is 6-10 h;
the first calcining comprises: heating to 250-300 ℃ at the rate of 40-60 ℃/h and keeping for 3-5h, heating to 700-800 ℃ at the rate of 110-130 ℃/h and keeping for 3-5 h;
the concentration of the metal oxide in the primary mixture is 85-160 g/L.
8. The method according to claim 6, wherein the cerium-zirconium solid solution in the step 2) is mixed with γ -Al2O3The mixing comprises the following steps: subjecting the gamma-Al to2O3Ball-milling for 8-12h under the protection of inert gas with the ball-material ratio of 8: 1 and the rotating speed of 250r/min, adding the cerium-zirconium solid solution, and continuing ball-milling for 5-25 h;
preferably, the first firing comprises: roasting at 800-900 deg.c for 1-5 hr.
9. The preparation method as claimed in claim 6, wherein the second calcination is carried out under conditions of calcination at 550 ℃ and 450 ℃ for 2-6 h.
10. Use of a three-way catalyst in a CO oxidation reaction, wherein the three-way catalyst is selected from the three-way catalysts of any one of claims 1 to 9.
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| CN113058598A (en) * | 2021-03-18 | 2021-07-02 | 北京工业大学 | Improved ALD method for depositing CeO2Method (2) |
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