CN111957312A - Catalyst for motor vehicle tail gas and preparation method and application thereof - Google Patents
Catalyst for motor vehicle tail gas and preparation method and application thereof Download PDFInfo
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- CN111957312A CN111957312A CN202010848565.0A CN202010848565A CN111957312A CN 111957312 A CN111957312 A CN 111957312A CN 202010848565 A CN202010848565 A CN 202010848565A CN 111957312 A CN111957312 A CN 111957312A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 67
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000002002 slurry Substances 0.000 claims abstract description 56
- 239000002131 composite material Substances 0.000 claims abstract description 53
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 53
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 38
- 239000006255 coating slurry Substances 0.000 claims abstract description 33
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 30
- 150000003754 zirconium Chemical class 0.000 claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 claims abstract description 26
- 239000000919 ceramic Substances 0.000 claims abstract description 26
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 26
- 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 compound [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 claims abstract description 26
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 21
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 21
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 21
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 20
- 238000011068 loading method Methods 0.000 claims abstract description 19
- 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 18
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 16
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 230000032683 aging Effects 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000008279 sol Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 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 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- 239000011268 mixed slurry Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910001868 water Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000006104 solid solution Substances 0.000 description 7
- 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 description 6
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 5
- 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 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 5
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 5
- 238000007664 blowing Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 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 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- -1 tungsten-silicon-aluminum Chemical compound 0.000 description 3
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
- B01J37/0215—Coating
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
-
- 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
-
- 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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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2370/00—Selection of materials for exhaust purification
- F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2510/00—Surface coverings
- F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
- F01N2510/065—Surface coverings for exhaust purification, e.g. catalytic reaction for reducing soot ignition temperature
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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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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Toxicology (AREA)
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- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for motor vehicle exhaust, a preparation method and application thereof. The preparation method comprises the following steps: (1) adding a solution containing a catalytic active element into the composite oxide slurry to obtain a first mixture; wherein, the catalytic active element is selected from one or more of platinum or palladium, the composite oxide slurry contains alumina and at least one other oxide, and the other oxide is selected from at least one of cerium oxide or zirconium oxide; (2) mixing raw materials containing the first mixture, soluble zirconium salt and a rare earth cocatalyst to obtain a second mixture; wherein, the rare earth elements in the rare earth cocatalyst are lanthanum and yttrium; (3) mixing the second mixture with a binder to obtain a coating slurry; (4) and loading the coating slurry on a cordierite honeycomb ceramic carrier, and then drying and roasting to obtain the catalyst for the tail gas of the motor vehicle. The catalyst obtained by the method has lower ignition temperature after high-temperature treatment.
Description
Technical Field
The invention relates to a catalyst for motor vehicle exhaust, a preparation method thereof and application of a composition.
Background
Pollutants discharged from tail gas of diesel vehicles contain hydrocarbons, carbon monoxide and particulate matters besides nitrogen oxides, and the pollutants seriously harm the health of human bodies and cause serious environmental pollution. The diesel vehicle oxidation catalyst technology can remove soluble organic matter components, hydrocarbons and nitric oxide in particles, and can convert a part of NO into NO2Thereby facilitating the subsequent reaction. The main active components of the diesel vehicle oxidation catalyst are precious metals such as platinum, palladium and the like, and the cost is high. In addition, the diesel vehicle oxidation catalyst is required to have higher high-temperature resistance in the use process, but the noble metal is easy to deactivate at high temperature. Therefore, the method has important significance for reducing the consumption of the noble metal, maintaining the low-temperature catalytic activity of the catalyst and improving the high-temperature resistance and aging resistance of the catalyst.
CN102039146A discloses a preparation method of a natural gas engine exhaust purification catalyst. The method comprises the following steps: mixing high-temperature stable active alumina, cerium-zirconium solid solution, rare earth oxide, alkaline earth metal oxide, a binder, water and at least one of transition metal composite oxide or transition metal-rare earth composite oxide as an active component to prepare coating slurry; coating the coating slurry on a cordierite honeycomb ceramic carrier on a coating machine, drying and roasting; dipping the cordierite honeycomb ceramic carrier containing the coating into an aqueous solution containing palladium salt and platinum salt by adopting an equal-volume dipping method, and drying and roasting the catalyst after dipping. The catalyst obtained by the method is not suitable for diesel vehicles, has poor high temperature resistance and aging resistance, and increases the ignition temperature after high-temperature treatment.
CN105797767A discloses a preparation method of diesel vehicle oxidation catalyst with low temperature activity. Which comprises the following steps: preparing an ammonium tungstate aqueous solution according to the saturated adsorption capacity of the silicon-aluminum composite, dropwise adding the prepared ammonium tungstate aqueous solution into the silicon-aluminum composite oxide, continuously stirring, standing, aging, drying, and roasting to obtain a tungsten-silicon-aluminum composite oxide; adding the tungsten-silicon-aluminum composite oxide and the molecular sieve into deionized water respectively, stirring to form slurry, and then treating the slurry by adopting a ball milling process to prepare coating slurry; adding a solution containing one or two of noble metals of Pt and Pd into the coating slurry, and uniformly stirring to form final slurry; and soaking a carrier cordierite ceramic honeycomb or an iron-chromium-aluminum metal honeycomb in the final slurry, taking out and roasting to obtain the diesel vehicle oxidation type catalyst. The catalyst has poor high temperature resistance and aging resistance, and the ignition temperature is increased after high-temperature treatment.
Disclosure of Invention
In view of the above, in one aspect, the present invention provides a method for preparing a catalyst for motor vehicle exhaust, which can obtain a catalyst having a lower light-off temperature after a high-temperature treatment. In another aspect, the present invention provides a catalyst for motor vehicle exhaust. In a further aspect, the invention provides the use of a composition.
The technical problem is solved by the following technical scheme.
In one aspect, the present invention provides a method for preparing a catalyst for motor vehicle exhaust, comprising the steps of:
(1) adding a solution containing a catalytic active element into the composite oxide slurry to obtain a first mixture; wherein the catalytic active element is selected from one or more of platinum or palladium, the composite oxide slurry contains alumina and at least one other oxide, and the other oxide is selected from at least one of cerium oxide or zirconium oxide;
(2) mixing raw materials containing the first mixture, soluble zirconium salt and a rare earth cocatalyst to obtain a second mixture; wherein, the rare earth elements in the rare earth cocatalyst are lanthanum and yttrium;
(3) mixing the second mixture with a binder to obtain a coating slurry;
(4) and loading the coating slurry on a cordierite honeycomb ceramic carrier, and then drying and roasting to obtain the catalyst for the tail gas of the motor vehicle.
According to the preparation method of the present invention, preferably, the solid content of the composite oxide slurry is 25 to 45 wt%, and the average value of the particle size of the solid particles in the composite oxide slurry is 1 to 10 μm.
According to the production method of the present invention, preferably, the composite oxide slurry contains alumina, ceria, and zirconia; wherein the mass ratio of the total mass of the cerium oxide and the zirconium oxide to the mass of the aluminum oxide is (0.08-0.2): 1, and the mass ratio of the cerium oxide to the zirconium oxide is (1-3): 2-5.
According to the preparation method provided by the invention, preferably, the volume of the cordierite honeycomb ceramic carrier is taken as a reference, and the loading amount of the catalytic active elements is 15-30 g/ft3Calculated by the simple substance of the catalytic active element.
According to the production method of the present invention, preferably, the catalytically active elements are platinum and palladium; the platinum element is calculated by a platinum simple substance, the palladium element is calculated by a palladium simple substance, and the mass ratio of the platinum element to the palladium element is (1-4): 1.
According to the preparation method of the invention, preferably, the amount of the rare earth cocatalyst is 2-7 wt% of the total mass of the oxides in the composite oxide slurry, and the rare earth cocatalyst is calculated by the rare earth oxides; the mass ratio of the lanthanum element to the yttrium element is 1 (0.5-2), the lanthanum element is calculated by lanthanum oxide, and the yttrium element is calculated by yttrium oxide.
According to the preparation method of the invention, preferably, the amount of the soluble zirconium salt is 1-7 wt% of the total mass of the oxides in the composite oxide slurry, and the soluble zirconium salt is calculated by zirconium oxide; the binder is selected from one or more of aluminum sol, pseudo-boehmite, silica sol, cellulose, citric acid, polyvinyl alcohol and polyethylene glycol.
In another aspect, the present invention provides a catalyst for motor vehicle exhaust gas, which is obtained according to the above-mentioned preparation method,
the temperatures of the fresh catalyst, the aged catalyst and the high-temperature treated catalyst which correspond to the CO conversion rate of 50 percent are 140-180 ℃, 140-180 ℃ and 140-180 ℃ respectively;
fresh catalyst, aged catalyst and high-temperature treated catalyst pair C3H6The temperature corresponding to the conversion rate of 50% is 180-200 ℃, 170-200 ℃ and 170-200 ℃ respectively;
the tests were carried out in a fixed bed reactorThe reaction conditions are as follows: CO 200ppm and C3H6＝180ppm、NO＝500ppm、CO2＝10vol％、O2＝10vol％，H2O＝7vol％、N2For balancing gas, the total flow is 550ml/min, and the space velocity is 80000h-1(ii) a The reaction temperature range is 100-500 ℃;
aging conditions are as follows: h2O is 10 vol% and the space velocity is 60000h-1The aging temperature is 650 ℃, and the aging time is 100 hours;
high-temperature treatment conditions: the high-temperature treatment is roasting at 800 ℃ for 3 h.
In another aspect, the present invention provides a method for preparing a catalyst for motor vehicle exhaust, comprising the steps of:
(1) adding a solution containing a catalytic active element into the composite oxide slurry to obtain a first mixture; wherein the catalytic active element is selected from one or more of platinum or palladium, the composite oxide slurry contains alumina and at least one other oxide, and the other oxide is selected from at least one of cerium oxide or zirconium oxide;
(2) mixing raw materials containing the first mixture, soluble zirconium salt and a rare earth cocatalyst to obtain a second mixture; wherein, the rare earth elements in the rare earth cocatalyst are lanthanum and yttrium;
(3) mixing the second mixture with a binder to obtain a coating slurry;
(4) loading the coating slurry on a cordierite honeycomb ceramic carrier, and then drying and roasting to obtain a roasted product;
(5) and (3) treating the roasted product at the high temperature of 780-1000 ℃ for 0.5-10 h to obtain the catalyst for the tail gas of the motor vehicle.
In yet another aspect, the present invention provides the use of a composition for reducing the light-off temperature of a high temperature treated motor vehicle exhaust catalyst, the composition comprising a rare earth promoter and a soluble zirconium salt, the rare earth element in the rare earth promoter being lanthanum and yttrium; the high-temperature treatment condition is to carry out high-temperature treatment for 0.5 to 10 hours at 780 to 1000 ℃.
The catalyst for the tail gas of the motor vehicle prepared by the method has lower ignition temperature. The applicant has surprisingly found that by adding a rare earth promoter consisting of lanthanum and yttrium and a soluble zirconium salt during the preparation of the catalyst, the obtained catalyst has a lower light-off temperature after high-temperature treatment.
Drawings
FIG. 1 is a graph of CO conversion as a function of temperature for the motor vehicle exhaust catalyst of example 1;
FIG. 2 shows catalyst C for motor vehicle exhaust gas of example 13H6A graph of conversion as a function of temperature;
FIG. 3 is a graph of CO conversion versus temperature for the catalyst of comparative example 1;
FIG. 4 shows catalyst C of comparative example 13H6A graph of conversion as a function of temperature;
FIG. 5 is a plot of CO conversion versus temperature for the catalyst of comparative example 2;
FIG. 6 shows catalyst C of comparative example 23H6A graph of conversion as a function of temperature;
Detailed Description
The present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
< method for producing catalyst for automobile exhaust gas >
The preparation method of the catalyst for the automobile exhaust comprises the following steps: (1) a step of forming a first mixture; (2) a step of forming a second mixture; (3) a step of preparing a coating slurry; (4) a step of preparing a catalyst; optionally, (5) a step of high temperature treatment.
Step of forming a first mixture
Adding a solution containing a catalytically active element to the composite oxide slurry to obtain a first mixture.
The composite oxide slurry is formed from at least two oxides and water. The oxide in the composite oxide slurry contains alumina and at least one other oxide. The other oxide is at least one selected from cerium oxide or zirconium oxide. In certain embodiments, the composite oxide slurry comprises alumina, ceria, and zirconia. According to one embodiment of the present invention, the composite oxide slurry contains alumina and a cerium-zirconium solid solution. The ratio of the total mass of the cerium oxide and the zirconium oxide to the mass of the aluminum oxide may be (0.08-0.2): 1; preferably (0.08-0.15): 1; more preferably (0.1 to 0.13): 1. The mass ratio of cerium oxide to zirconium oxide may be (1-3) to (2-5); preferably (1-2) to (2-4); more preferably 2 (3-4). Thus, the ignition temperature of the catalyst is reduced, and the aging resistance and high temperature resistance of the catalyst are improved.
The solid content of the composite oxide slurry can be 25-45 wt%; preferably 30 to 40 wt%; more preferably 33 to 37 wt%. The average value of the particle size of solid particles in the composite oxide slurry can be 1-10 mu m; preferably 3-8 μm; more preferably 4 to 7 μm.
The catalytic active element is at least one selected from platinum and palladium. Based on the volume of the cordierite honeycomb ceramic carrier, the loading capacity of the catalytic active elements can be 15-30 g/ft by the simple substance of the catalytic active elements3(ii) a Preferably 20 to 30g/ft3(ii) a More preferably 23 to 27g/ft3. The catalytic active element can be dripped into the composite oxide slurry in the form of soluble salt solution; preferably, a solution of a soluble salt containing a catalytically active element is added dropwise to the slurry of the composite oxide under stirring. The mass fraction of solute in the soluble salt solution containing the catalytic active elements can be 10-25 wt%; preferably 15 to 25 wt%; more preferably 15 to 20 wt%. The soluble salt containing the catalytically active element may be a nitrate salt, such as palladium nitrate, platinum nitrate. Preferably, the catalytically active elements are palladium and platinum. The platinum element is calculated by a platinum simple substance, the palladium element is calculated by a palladium simple substance, and the mass ratio of the platinum element to the palladium element can be (1-4): 1; preferably (1-3) 1; more preferably (2-3): 1. Thus, the ignition temperature of the catalyst is reduced, and the aging resistance and high temperature resistance of the catalyst are improved.
Step of forming a second mixture
Mixing the raw materials containing the first mixture, a soluble zirconium salt and a rare earth promoter to obtain a second mixture. In certain embodiments, the feedstock consists of the first mixture, a soluble zirconium salt, and a rare earth promoter.
The rare earth promoter in the invention is selected from one or more of soluble inorganic salts or oxides of rare earth elements. The soluble inorganic salt may be nitrate, sulphate, acetate or chloride. The rare earth element is lanthanum element and yttrium element. Examples of rare earth promoters include, but are not limited to: lanthanum chloride, yttrium chloride, lanthanum nitrate, yttrium nitrate, lanthanum oxide and yttrium oxide. In terms of rare earth oxidation, the using amount of the rare earth cocatalyst is 2-7 wt% of the total mass of the oxides in the composite oxide slurry; preferably 3-6 wt%; more preferably 3 to 5 wt%. The lanthanum element is calculated by lanthanum oxide, the yttrium element is calculated by yttrium oxide, and the mass ratio of the lanthanum element to the yttrium element can be 1 (0.5-2); preferably 1 (0.5-1.5); more preferably 1 (1-1.5). Thus, the ignition temperature of the catalyst is reduced, and the aging resistance and high temperature resistance of the catalyst are improved.
The soluble zirconium salt can be selected from one or more of zirconium acetate, zirconium nitrate and zirconium chloride; preferably zirconium acetate. Based on the zirconium oxide, the amount of the soluble zirconium salt is 1-7 wt% of the total mass of the oxides in the composite oxide slurry; preferably 2-6 wt%; more preferably 2 to 4 wt%. The soluble zirconium salt can be used in the form of solution, and the mass fraction of solute in the soluble zirconium salt can be 15-30 wt%; preferably 17-25 wt%; more preferably 20 to 25 wt%. Thus, the ignition temperature of the catalyst is reduced, and the aging resistance and high temperature resistance of the catalyst are improved.
Step of preparing coating slurry
The second mixture is mixed with a binder to obtain a coating slurry.
The binder can be one or more selected from aluminum sol, pseudo-boehmite, silica sol, cellulose, citric acid, polyvinyl alcohol and polyethylene glycol. Preferably, the binder is selected from one or more of aluminum sol, pseudo-boehmite, silica sol. More preferably, the binder is an aluminum sol. The using amount of the binder is 45-75 wt% of the total mass of the oxides in the composite oxide slurry; preferably 50 to 70 wt%; more preferably 55 to 65 wt%.
Step of preparing the catalyst
And loading the coating slurry on a cordierite honeycomb ceramic carrier, and then drying and roasting to obtain the catalyst for the tail gas of the motor vehicle.
The drying temperature can be 90-130 ℃; preferably 100-130 ℃; more preferably 100 to 120 ℃. The drying time can be 2-6 h; preferably 2-5 h; more preferably 2 to 4 hours.
The roasting temperature can be 500-750 ℃; preferably 500-700 ℃; more preferably 500 to 600 ℃. The roasting time can be 2-6 h, preferably 2-5 h; more preferably 2 to 4 hours.
The total loading capacity of each element in the coating slurry on the cordierite honeycomb ceramic carrier is 150-180 g/L calculated by oxide; preferably 150-170 g/L; more preferably 155 to 165 g/L.
Step of high temperature treatment
The method for preparing the catalyst for automobile exhaust gas of the present invention may include the steps of:
(1) adding a solution containing a catalytic active element into the composite oxide slurry to obtain a first mixture; wherein the catalytic active element is selected from one or more of platinum or palladium, the composite oxide slurry contains alumina and at least one other oxide, and the other oxide is selected from at least one of cerium oxide or zirconium oxide;
(2) mixing raw materials containing the first mixture, soluble zirconium salt and a rare earth cocatalyst to obtain a second mixture; wherein, the rare earth elements in the rare earth cocatalyst are lanthanum and yttrium;
(3) mixing the second mixture with a binder to obtain a coating slurry;
(4) loading the coating slurry on a cordierite honeycomb ceramic carrier, and then drying and roasting to obtain a roasted product;
(5) and (3) treating the roasted product at the high temperature of 780-1000 ℃ for 0.5-10 h to obtain the catalyst for the tail gas of the motor vehicle.
Steps (1) to (4) are as described above. In the step (5), the temperature of the high-temperature treatment can be 780-1000 ℃, preferably 800-950 ℃, and more preferably 800-900 ℃. The time of the high-temperature treatment can be 0.5-10 h, preferably 1-8 h, and more preferably 2-5 h. This is advantageous in reducing the light-off temperature of the catalyst.
< catalyst for exhaust gas of Motor vehicle >
The catalyst for motor vehicle exhaust gas is prepared by the method. The corresponding temperature of the fresh catalyst to the CO conversion rate of 50% is 140-180 ℃; preferably 150-180 ℃; more preferably 170 to 180 ℃. The temperature of the aged catalyst is 140-180 ℃ when the CO conversion rate is 50%; preferably 160-175 ℃; more preferably 165 to 175 ℃. The temperature corresponding to the CO conversion rate of the catalyst after high-temperature treatment is 140-180 ℃; preferably 160-175 ℃; more preferably 165 to 170 ℃. Fresh catalyst pair C3H6The temperature is 180-200 ℃ when the conversion rate is 50%; preferably 190-200 ℃; more preferably 195 to 200 ℃. Aged catalyst pair C3H6The temperature is 170-200 ℃ when the conversion rate is 50%; preferably 180-200 ℃; more preferably 190 to 200 ℃. Catalyst pair C after high-temperature treatment3H6The temperature is 170-200 ℃ when the conversion rate is 50%; preferably 180-200 ℃; more preferably 185 to 190 ℃.
The test conditions were as follows:
the test was carried out in a fixed bed reactor under the following reaction conditions: CO 200ppm and C3H6＝180ppm、NO＝500ppm、CO2＝10vol％、O2＝10vol％，H2O＝7vol％、N2For balancing gas, the total flow is 550ml/min, and the space velocity is 80000h-1(ii) a The reaction temperature range is 100-500 ℃;
aging conditions are as follows: H2O is 10 vol%, space velocity is 60000H-1, aging temperature is 650 ℃, and aging time is 100H;
high-temperature treatment conditions: roasting at 800 deg.c for 3 hr.
< uses of the composition >
Applicants have unexpectedly found that compositions comprising a rare earth promoter and a soluble zirconium salt are capable of reducing the light-off temperature of catalysts for automotive exhaust after aging and/or after high temperature treatment. Accordingly, the present invention provides the use of a composition for reducing the light-off temperature of a high temperature treated catalyst for motor vehicle exhaust.
The composition of the invention comprises a rare earth promoter and a soluble zirconium salt. The composition may consist of a rare earth adjuvant and a soluble zirconium salt.
The rare earth promoter is selected from one or more of soluble inorganic salts or oxides of rare earth elements. The soluble inorganic salt may be nitrate, sulphate, acetate or chloride. The rare earth element is lanthanum element and yttrium element. Examples of rare earth promoters include, but are not limited to: lanthanum chloride, yttrium chloride, lanthanum nitrate, yttrium nitrate, lanthanum oxide and yttrium oxide. In terms of rare earth oxidation, the using amount of the rare earth cocatalyst is 2-7 wt% of the total mass of the oxides in the composite oxide slurry; preferably 3-6 wt%; more preferably 3 to 5 wt%. The lanthanum element is calculated by lanthanum oxide, the yttrium element is calculated by yttrium oxide, and the mass ratio of the lanthanum element to the yttrium element can be 1 (0.5-2); preferably 1 (0.5-1.5); more preferably 1 (1-1.5).
The soluble zirconium salt can be selected from one or more of zirconium acetate, zirconium nitrate and zirconium chloride; preferably zirconium acetate. Based on the zirconium oxide, the amount of the soluble zirconium salt is 1-7 wt% of the total mass of the oxides in the composite oxide slurry; preferably 2-6 wt%; more preferably 2 to 4 wt%. The soluble zirconium salt can be used in the form of solution, and the mass fraction of solute in the soluble zirconium salt can be 15-30 wt%; preferably 17-25 wt%; more preferably 20 to 25 wt%.
In some embodiments, the method specifically comprises the following steps:
(1) adding a solution containing a catalytic active element into the composite oxide slurry to obtain a first mixture; wherein the catalytic active element is selected from one or more of platinum or palladium, the composite oxide slurry contains alumina and at least one other oxide, and the other oxide is selected from at least one of cerium oxide or zirconium oxide;
(2) mixing raw materials containing the first mixture, soluble zirconium salt and a rare earth cocatalyst to obtain a second mixture; wherein, the rare earth elements in the rare earth cocatalyst are lanthanum and yttrium;
(3) mixing the second mixture with a binder to obtain a coating slurry;
(4) and loading the coating slurry on a cordierite honeycomb ceramic carrier, and then drying and roasting to obtain the catalyst for the tail gas of the motor vehicle.
In some embodiments, the method specifically comprises the following steps:
(1) adding a solution containing a catalytic active element into the composite oxide slurry to obtain a first mixture; wherein the catalytic active element is selected from one or more of platinum or palladium, the composite oxide slurry contains alumina and at least one other oxide, and the other oxide is selected from at least one of cerium oxide or zirconium oxide;
(2) mixing raw materials containing the first mixture, soluble zirconium salt and a rare earth cocatalyst to obtain a second mixture; wherein, the rare earth elements in the rare earth cocatalyst are lanthanum and yttrium;
(3) mixing the second mixture with a binder to obtain a coating slurry;
(4) loading the coating slurry on a cordierite honeycomb ceramic carrier, and then drying and roasting to obtain a roasted product;
(5) and (3) treating the roasted product at the high temperature of 780-1000 ℃ for 0.5-10 h to obtain the catalyst for the tail gas of the motor vehicle.
The parameters of the above steps and the parameters of the raw materials are as described above.
The following raw materials are introduced:
the cerium-zirconium solid solution contained zirconium in an amount of 60 wt% (in terms of zirconium oxide) and cerium in an amount of 40 wt% (in terms of cerium oxide).
Example 1
786g of alumina, 87g of a cerium-zirconium solid solution and water were uniformly mixed to form a mixed slurry, the solid content of the mixed slurry was 35 wt%, and the mixed slurry was ball-milled until the average particle size of solid particles in the mixed slurry was 5 μm, to obtain a composite oxide slurry.
To the composite oxide slurry were added dropwise, while stirring, 13g of a palladium nitrate solution (mass fraction of palladium element: 17.4 wt%) and 25.6g of a platinum nitrate solution (mass fraction of platinum element: 17.7 wt%), respectively, to obtain a first mixture.
To the first mixture were added 53g of lanthanum nitrate, 68g of yttrium nitrate and 318g of a zirconium acetate solution (mass fraction: 22 wt%), to obtain a second mixture.
To the second mixture was added 500g of an aluminum sol to obtain a coating slurry.
Immersing the cordierite honeycomb ceramic carrier into the coating slurry, taking out and blowing redundant slurry; then drying the mixture for 3 hours at the temperature of 110 ℃, and roasting the dried cordierite honeycomb ceramic for 3 hours at the temperature of 550 ℃ to obtain the catalyst for the tail gas of the motor vehicle (the loading amount of the catalyst is 160g/L calculated by oxide, and the total loading amount of palladium element and platinum element is 25 g/ft)3)。
Comparative example 1
894g of alumina, 99g of cerium-zirconium solid solution and water are uniformly mixed to form mixed slurry, the solid content of the mixed slurry is 35 wt%, and the mixed slurry is ball-milled until the average particle size of solid particles in the mixed slurry is 5 μm, so that composite oxide slurry is obtained.
To the composite oxide slurry were added dropwise, while stirring, 13g of a palladium nitrate solution (mass fraction of palladium element: 17.4 wt%) and 25.6g of a platinum nitrate solution (mass fraction of platinum element: 17.7 wt%), respectively, to obtain a first mixture.
To the first mixture was added 500g of an aluminum sol to obtain a coating slurry.
Immersing the cordierite honeycomb ceramic carrier into the coating slurry, taking out and blowing redundant slurry; then drying the cordierite honeycomb ceramic for 3 hours at the temperature of 110 ℃, and roasting the dried cordierite honeycomb ceramic for 3 hours at the temperature of 550 ℃ to obtain a catalyst (the loading amount of the catalyst is 160g/L calculated by oxide, and the total loading amount of palladium element and platinum element is 25g/ft3)。
Comparative example 2
809g of alumina, 94g of cerium-zirconium solid solution and water are uniformly mixed to form mixed slurry, the solid content of the mixed slurry is 35 wt%, and the mixed slurry is ball-milled until the average particle size of solid particles in the mixed slurry is 5 μm, so that the composite oxide slurry is obtained.
To the composite oxide slurry were added dropwise, while stirring, 13g of a palladium nitrate solution (mass fraction of palladium element: 17.4 wt%) and 25.6g of a platinum nitrate solution (mass fraction of platinum element: 17.7 wt%), respectively, to obtain a first mixture.
53g of lanthanum nitrate and 68g of yttrium nitrate were added to the first mixture to obtain a second mixture.
To the second mixture was added 500g of an aluminum sol to obtain a coating slurry.
Immersing the cordierite honeycomb ceramic carrier into the coating slurry, taking out and blowing redundant slurry; then drying for 3h at 110 ℃, and roasting the dried cordierite honeycomb ceramic for 3h at 550 ℃ to obtain a catalyst (the loading capacity of the catalyst is 160g/L and the total loading amount of palladium element and platinum element is 25g/ft in terms of oxide)3)。
Examples of the experiments
The catalysts prepared in the above examples and comparative examples were tested for CO and C3H6The temperature at which the conversion is 50%.
The test was carried out in a fixed bed reactor under the following reaction conditions: CO 200ppm and C3H6＝180ppm、NO＝500ppm、CO2＝10vol％、O2＝10vol％，H2O＝7vol％、N2For balancing gas, the total flow is 550ml/min, and the space velocity is 80000h-1(ii) a The reaction temperature range is 100-500 ℃.
Aging conditions are as follows: h2O is 10 vol% and the space velocity is 60000h-1The aging temperature is 650 ℃, and the aging time is 100 h.
High-temperature treatment conditions: the high temperature treatment was carried out in a muffle furnace and calcined at 800 ℃ for 3 h. The test results are shown in Table 1 and FIGS. 1 to 6.
TABLE 1
As can be seen from Table 1, in comparison with comparative examples 1 and 2, the light-off temperature of the catalyst for motor vehicle exhaust gas of the present invention is significantly lower than that of the catalysts of comparative examples 1 and 2, and the catalyst of the present invention has a lower light-off temperature in an aged state and a fresher state after being subjected to a high temperature treatment.
Example 2
786g of alumina, 87g of a cerium-zirconium solid solution and water were uniformly mixed to form a mixed slurry, the solid content of the mixed slurry was 35 wt%, and the mixed slurry was ball-milled until the average particle size of solid particles in the mixed slurry was 5 μm, to obtain a composite oxide slurry.
To the composite oxide slurry were added dropwise, while stirring, 13g of a palladium nitrate solution (mass fraction of palladium element: 17.4 wt%) and 25.6g of a platinum nitrate solution (mass fraction of platinum element: 17.7 wt%), respectively, to obtain a first mixture.
To the first mixture were added 53g of lanthanum nitrate, 68g of yttrium nitrate and 318g of a zirconium acetate solution (mass fraction: 22 wt%), to obtain a second mixture.
To the second mixture was added 500g of an aluminum sol to obtain a coating slurry.
Immersing the cordierite honeycomb ceramic carrier into the coating slurry, taking out and blowing redundant slurry; then drying the cordierite honeycomb ceramic for 3 hours at the temperature of 110 ℃, and roasting the dried cordierite honeycomb ceramic for 3 hours at the temperature of 550 ℃ to obtain a roasted product;
and placing the roasted product in a muffle furnace, and roasting for 3 hours at 800 ℃ to obtain the catalyst for the tail gas of the motor vehicle. See table 1 for properties.
The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the invention.
Claims (10)
1. A preparation method of a catalyst for motor vehicle exhaust is characterized by comprising the following steps:
(1) adding a solution containing a catalytic active element into the composite oxide slurry to obtain a first mixture; wherein the catalytic active element is selected from one or more of platinum or palladium, the composite oxide slurry contains alumina and at least one other oxide, and the other oxide is selected from at least one of cerium oxide or zirconium oxide;
(2) mixing raw materials containing the first mixture, soluble zirconium salt and a rare earth cocatalyst to obtain a second mixture; wherein, the rare earth elements in the rare earth cocatalyst are lanthanum and yttrium;
(3) mixing the second mixture with a binder to obtain a coating slurry;
(4) and loading the coating slurry on a cordierite honeycomb ceramic carrier, and then drying and roasting to obtain the catalyst for the tail gas of the motor vehicle.
2. The production method according to claim 1, wherein the solid content of the composite oxide slurry is 25 to 45 wt%, and the average value of the particle sizes of the solid particles in the composite oxide slurry is 1 to 10 μm.
3. The production method according to claim 1, wherein the composite oxide slurry contains alumina, ceria, and zirconia; wherein the mass ratio of the total mass of the cerium oxide and the zirconium oxide to the mass of the aluminum oxide is (0.08-0.2): 1, and the mass ratio of the cerium oxide to the zirconium oxide is (1-3): 2-5.
4. The preparation method according to claim 1, wherein the volume of the cordierite honeycomb ceramic carrier is taken as a reference, and the loading amount of the catalytic active elements is 15-30 g/ft3Calculated by the simple substance of the catalytic active element.
5. The production method according to claim 4, wherein the catalytically active elements are platinum and palladium; the platinum element is calculated by a platinum simple substance, the palladium element is calculated by a palladium simple substance, and the mass ratio of the platinum element to the palladium element is (1-4): 1.
6. The preparation method according to claim 1, wherein the amount of the rare earth promoter is 2-7 wt% of the total mass of the oxides in the composite oxide slurry, and the rare earth promoter is calculated by the rare earth oxide; the mass ratio of the lanthanum element to the yttrium element is 1 (0.5-2), the lanthanum element is calculated by lanthanum oxide, and the yttrium element is calculated by yttrium oxide.
7. The method according to claim 1, wherein the amount of the soluble zirconium salt is 1 to 7 wt% based on the total mass of the oxides in the composite oxide slurry, and the soluble zirconium salt is calculated as zirconium oxide; the binder is selected from one or more of aluminum sol, pseudo-boehmite, silica sol, cellulose, citric acid, polyvinyl alcohol and polyethylene glycol.
8. A catalyst for automobile exhaust gas, which is obtained by the production method according to any one of claims 1 to 7,
the temperatures of the fresh catalyst, the aged catalyst and the high-temperature treated catalyst which correspond to the CO conversion rate of 50 percent are 140-180 ℃, 140-180 ℃ and 140-180 ℃ respectively;
fresh catalyst, aged catalyst and high-temperature treated catalyst pair C3H6The temperature corresponding to the conversion rate of 50% is 180-200 ℃, 170-200 ℃ and 170-200 ℃ respectively;
the test was carried out in a fixed bed reactor under the following reaction conditions: CO 200ppm and C3H6＝180ppm、NO＝500ppm、CO2＝10vol％、O2＝10vol％，H2O＝7vol％、N2For balancing gas, the total flow is 550ml/min, and the space velocity is 80000h-1(ii) a The reaction temperature range is 100-500 ℃;
aging conditions are as follows: h2O is 10 vol% and the space velocity is 60000h-1The aging temperature is 650 ℃, and the aging time is 100 hours;
high-temperature treatment conditions: the high-temperature treatment is roasting at 800 ℃ for 3 h.
9. A preparation method of a catalyst for motor vehicle exhaust is characterized by comprising the following steps:
(1) adding a solution containing a catalytic active element into the composite oxide slurry to obtain a first mixture; wherein the catalytic active element is selected from one or more of platinum or palladium, the composite oxide slurry contains alumina and at least one other oxide, and the other oxide is selected from at least one of cerium oxide or zirconium oxide;
(2) mixing raw materials containing the first mixture, soluble zirconium salt and a rare earth cocatalyst to obtain a second mixture; wherein, the rare earth elements in the rare earth cocatalyst are lanthanum and yttrium;
(3) mixing the second mixture with a binder to obtain a coating slurry;
(4) loading the coating slurry on a cordierite honeycomb ceramic carrier, and then drying and roasting to obtain a roasted product;
(5) and (3) treating the roasted product at the high temperature of 780-1000 ℃ for 0.5-10 h to obtain the catalyst for the tail gas of the motor vehicle.
10. The application of a composition in reducing the ignition temperature of a catalyst for motor vehicle exhaust after high-temperature treatment is characterized in that the composition comprises a rare earth cocatalyst and a soluble zirconium salt, wherein the rare earth elements in the rare earth cocatalyst are lanthanum element and yttrium element; the high-temperature treatment condition is to carry out high-temperature treatment for 0.5 to 10 hours at 780 to 1000 ℃.
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| CN113376310A (en) * | 2021-06-17 | 2021-09-10 | 上海松柏传感技术有限公司 | Preparation method of gas-sensitive material for combustible gas sensor and product |
| CN114849697A (en) * | 2022-05-23 | 2022-08-05 | 东风汽车集团股份有限公司 | Catalyst based on three-way catalyst ceramic carrier and preparation method thereof |
| CN116099533A (en) * | 2022-12-31 | 2023-05-12 | 中国船舶重工集团公司第七一八研究所 | Integral catalyst for methane combustion and preparation and application thereof |
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| CN114849697B (en) * | 2022-05-23 | 2023-10-27 | 东风汽车集团股份有限公司 | Catalyst based on three-way catalyst ceramic carrier and preparation method thereof |
| CN116099533A (en) * | 2022-12-31 | 2023-05-12 | 中国船舶重工集团公司第七一八研究所 | Integral catalyst for methane combustion and preparation and application thereof |
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