CN111921540B - Preparation method of three-way catalyst for automobile exhaust, product and application thereof - Google Patents
Preparation method of three-way catalyst for automobile exhaust, product and application thereof Download PDFInfo
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- CN111921540B CN111921540B CN202010852759.8A CN202010852759A CN111921540B CN 111921540 B CN111921540 B CN 111921540B CN 202010852759 A CN202010852759 A CN 202010852759A CN 111921540 B CN111921540 B CN 111921540B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 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 22
- 230000032683 aging Effects 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 34
- 239000000084 colloidal system Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 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 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 16
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- APRNQTOXCXOSHO-UHFFFAOYSA-N lutetium(3+);trinitrate Chemical compound [Lu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O APRNQTOXCXOSHO-UHFFFAOYSA-N 0.000 claims description 11
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims description 11
- ODKSFYDXXFIFQN-BYPYZUCNSA-N L-arginine Chemical compound OC(=O)[C@@H](N)CCCN=C(N)N ODKSFYDXXFIFQN-BYPYZUCNSA-N 0.000 claims description 10
- 229930064664 L-arginine Natural products 0.000 claims description 10
- 235000014852 L-arginine Nutrition 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 229910003244 Na2PdCl4 Inorganic materials 0.000 claims description 7
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 229910001868 water Inorganic materials 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 35
- 239000006104 solid solution Substances 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052765 Lutetium Inorganic materials 0.000 abstract description 9
- 229910052769 Ytterbium Inorganic materials 0.000 abstract description 9
- 229910052802 copper Inorganic materials 0.000 abstract description 9
- 239000010949 copper Substances 0.000 abstract description 9
- 229910000510 noble metal Inorganic materials 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 abstract description 8
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 229910052763 palladium Inorganic materials 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 5
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 10
- 238000011068 loading method Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- -1 oxygen ions Chemical class 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000010970 precious metal Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 230000002195 synergetic effect Effects 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 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
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
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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
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Combustion & Propulsion (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a preparation method of a three-way catalyst for automobile exhaust, a product and application thereof. The invention coats palladium with a solid solution material, then loads the solid solution material on copper modified alumina, wherein the solid solution is cerium zirconium solid solution modified by ytterbium and lutetium, and then carries out steam treatment, wherein the palladium coated by the solid solution can obviously prevent the agglomeration of noble metal palladium, moreover, the oxygen storage and release performance and the thermal stability of the catalyst can be improved due to the modification of ytterbium and lutetium, and the copper modified alumina surface has a grid structure, so that the use amount of noble metal can be reduced, the performance of the catalyst can be improved, the ignition temperature can be reduced, the hydrothermal stability and the catalytic activity of the catalyst can be enhanced through the aging treatment of steam, and the copper modified alumina is an ideal material for treating automobile exhaust.
Description
Technical Field
The invention relates to the field of automobile exhaust treatment, in particular to a preparation method of a three-way catalyst for automobile exhaust, a product and application thereof.
Background
It is generally known that the main pollutants of automobile exhaust gas are carbon monoxide (CO), Hydrocarbons (HC) and Nitrogen Oxides (NO)x) Three components. And automobile exhaust's emission seriously pollutes the air, is the main reason for luring haze weather formation, and it has seriously influenced traffic safety and human health, causes very big unfavorable to life production, so, reduces automobile exhaust pollutant's emission, is the important problem that needs to solve at present urgently.
Application of three-way catalyst technology in realizing conversion of automobile exhaust into nontoxic CO2And H2O provides an effective measure. The cerium-based material is an important component of the three-way catalyst, and plays roles in storing/releasing oxygen, improving the dispersion degree of noble metals, promoting water-vapor conversion and steam reforming reactions, and the like. In CeO2Zr is added into the material, so that the oxygen storage performance and the ageing resistance of the cerium-based material can be improved, however, with the stricter emission regulations, the requirements on the low-temperature activity and the high-temperature ageing resistance of the catalyst are higher and higher, so that the important direction of the research on the catalyst is to improve the ageing resistance of the material and enhance the mobility of oxygen ions.
Platinum group metals (Pt, Rh and Pd) of an automobile exhaust catalyst are main active components of a three-way catalyst, however, precious metal resources in China are deficient and mainly depend on import, so that the price of the precious metal is increased, and therefore, in the face of the contradiction between the weak supply and the high demand of the precious metal resources, the aim of reducing the use of the precious metal is achieved under the condition of ensuring that the emission standard is met.
Based on the above situation, there is an urgent need to develop a new three-way catalyst which has low light-off temperature and excellent catalytic performance on the premise of reducing the noble metal load, and still remains a technical problem which needs to be solved at present.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a three-way catalyst for automobile exhaust, a product and an application thereof aiming at the defects in the prior art. According to the invention, palladium is coated on a solid solution material and then loaded on copper modified alumina, wherein the solid solution is cerium-zirconium solid solution modified by ytterbium and lutetium, and then water vapor treatment is carried out, so that agglomeration of noble metal palladium can be obviously prevented by coating palladium on the solid solution, moreover, because ytterbium and lutetium are modified, the oxygen storage and release performance and the thermal stability of the catalyst can be improved, and because the surface of copper modified alumina has a grid structure, the performance of the catalyst can be improved while the consumption of noble metals is reduced, the ignition temperature is reduced, and the hydrothermal stability and the catalytic activity of the catalyst can be enhanced by aging treatment of water vapor.
The invention adopts the following technical scheme:
a preparation method of a three-way catalyst for automobile exhaust comprises the following steps:
(1) soaking aluminum oxide particles with the diameter of 1.5mm in 50.0mL of mixed aqueous solution containing copper nitrate and urea, carrying out heat treatment at 60-90 ℃ for 12-24 hours, filtering, washing, drying, and roasting to obtain a copper-modified aluminum oxide carrier;
(2) adding PVP, ascorbic acid and KCl into ultrapure water at 70-90 DEG CoC, stirring in an oil bath for 5-20 min, and adding 1-3 mmol/L Na2PdCl4Adding the solution, and continuing to add the solution at 70-90 DEGoStirring for 2-4 h in an oil bath, then alternately washing with acetone and ethanol, and dispersing in ethanol to obtain Pd colloid;
(3) dissolving ytterbium nitrate, lutetium nitrate, cerium nitrate and zirconium nitrate in an ethanol water solution, adding the Pd colloid in the step (2) into a beaker, adding an L-arginine solution, fully stirring for 2-4 h at 70-90 ℃, washing for 3-5 times with acetone, carrying out centrifugal separation, and dispersing in ethanol to obtain a colloid (I);
(4) adding the copper-modified alumina carrier in the step (1) into the colloid (I) in the step (3), stirring for 2-4 h at room temperature, drying in an oven, roasting in a muffle furnace, and aging in a gas containing water vapor for 4-6 h at 1000-1100 ℃ to prepare an aged three-way catalyst; wherein the load of Pd is 0.01-0.08 wt%.
Preferably, in the step (1), the molar ratio of the aluminum oxide to the copper nitrate is 10-20: 1; the molar ratio of the urea to the copper nitrate is 6-10: 1.
Preferably, in the step (1), the drying is carried out at 100-130 ℃ for 6-12 hours; the roasting is carried out at 400-500 ℃ for 2-6 hours.
Preferably, in the step (2), the ultrapure water, PVP, ascorbic acid, KCl and Na2PdCl4The proportion of the solution is 7-9 mL: 45-55 mg; 55-65 mg; 185-200 mg: 2-4 mL; the volume of the ethanol is 8-12 mL.
Preferably, in the step (3), the volume ratio of the ethanol to the water is 1: 1; the volume of the ethanol water is 40-60 mL; the volume of the ethanol is 8-12 mL.
Preferably, in the step (3), the molar ratio of ytterbium nitrate, lutetium nitrate, cerium nitrate and zirconium nitrate is: 0.01-0.03: 1: 1; the mass ratio of the Pd colloid to the L-arginine is 1: 1.5-2; the mole ratio of the Pd colloid to the cerium nitrate is 1: 0.4-0.6.
Preferably, in the step (4), the drying is carried out at 70-90 ℃ for 12-24 h; the roasting is carried out at the temperature of 450-550 ℃ for 2-4 h.
Preferably, in the step (4), the gas containing water vapor is a mixed gas of water vapor and air, and the volume content of the water vapor is 8-12%.
The invention also provides a three-way catalyst for automobile exhaust, which is prepared based on the preparation method.
According to another technical scheme, based on the application of the three-way catalyst for the automobile exhaust, 150-250 mg of the catalyst with the particle size of 40-60 meshes is loaded into a fixed bed reactor by taking simulated automobile exhaust as a reaction atmosphere, and the automobile exhaust comprises 1.5-2% of CO and 0.2-0.3% of H2、450~550ppm HC(C3H8/C3H6=2:1)，900~1100ppm NO，1~2% O2，N2The reaction space velocity is 300 L.h for the balance gas-1·gcat -1。
The preparation method of the three-way catalyst for the automobile exhaust, the product and the application thereof have the following technical effects:
(1) copper, a divalent metal, can be used as catalytic NO by introducing copper nitrate in an aqueous solution containing ureaxThe active component reduces the reaction temperature, and the other part is used for modulating the surface structure of the alumina, so that the surface of the carrier forms a grid structure, the loading and the dispersion of the active component are facilitated, the catalytic performance is improved, and the loading of the noble metal is reduced.
(2) The Pd is coated by the solid solution, so that the agglomeration, growth and sintering of the noble metal can be obviously reduced, the loading capacity of the noble metal is further reduced, and the high-temperature thermal stability of the three-way catalyst is also improved.
(3) The cerium-zirconium solid solution modified by ytterbium and lutetium can generate lattice defects and oxygen ion cavities, and the synergistic effect of ytterbium and lutetium can obviously improve the oxygen storage and storage performance, improve the ageing resistance of the material, reduce the ignition temperature and improve the catalytic activity.
(4) According to the method, a large number of OH groups are arranged on the surface of the three-way catalyst through aging treatment of water vapor, and due to the existence of the OH groups, the surface activation energy of the three-way catalyst is reduced, so that the catalytic activity of the three-way catalyst is improved.
In conclusion, the three-way catalyst for the automobile exhaust prepared by the invention has excellent performance and excellent treatment capability on the automobile exhaust, and is an ideal material for treating the automobile exhaust.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. The components of the embodiments of the present invention generally shown may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a three-way catalyst for automobile exhaust comprises the following steps:
(1) soaking alumina particles with the diameter of 1.5mm in 50.0mL of mixed aqueous solution containing copper nitrate and urea, carrying out heat treatment at 80 ℃ for 20 hours, filtering, washing, drying at 110 ℃ for 10 hours, and roasting at 450 ℃ for 4 hours to obtain a copper-modified alumina carrier; the molar ratio of the aluminum oxide to the copper nitrate is 15: 1; the molar ratio of the urea to the copper nitrate is 8: 1;
(2) to 8mL of ultrapure water was added 50mg of PVP, 60mg of ascorbic acid and 195mg of KCl at 80oStirring in C oil bath for 15min, adding 3mL of 2 mmol/L Na2PdCl4The solution addition was continued at 80 deg.CoStirring for 3 hours in an oil bath, then alternately washing with acetone and ethanol, and dispersing in 10mL of ethanol to obtain Pd colloid;
(3) dissolving ytterbium nitrate, lutetium nitrate, cerium nitrate and zirconium nitrate in 50mL of ethanol water solution, wherein the volume ratio of ethanol to water is 1:1, adding the Pd colloid in the step (2) into a beaker, adding an L-arginine solution, fully stirring for 3h at 80 ℃, washing for 4 times by using acetone, carrying out centrifugal separation, and dispersing in 10mL of ethanol to obtain colloid (I); the molar ratio of ytterbium nitrate to lutetium nitrate to cerium nitrate to zirconium nitrate is as follows: 0.02:0.02:1: 1; the mass ratio of the Pd colloid to the L-arginine is 1: 1.6; the molar ratio of the Pd colloid to the cerium nitrate is 1: 0.5;
(4) adding the copper-modified alumina carrier in the step (1) into the colloid (I) in the step (3), stirring for 3h at room temperature, drying for 20h at 80 ℃ in a drying oven, then roasting for 3h at 500 ℃ in a muffle furnace, and aging for 5h at 1050 ℃ in a mixed gas of water vapor and air, wherein the volume content of the water vapor is 10%, so as to prepare an aged three-way catalyst; wherein the loading of Pd was 0.05 wt%.
Example 2
A preparation method of a three-way catalyst for automobile exhaust comprises the following steps:
(1) soaking alumina particles with the diameter of 1.5mm in 50.0mL of mixed aqueous solution containing copper nitrate and urea, carrying out heat treatment at 90 ℃ for 12 hours, filtering, washing, drying at 130 ℃ for 6 hours, and roasting at 500 ℃ for 2 hours to obtain a copper-modified alumina carrier; the molar ratio of the aluminum oxide to the copper nitrate is 20: 1; the molar ratio of the urea to the copper nitrate is 10: 1;
(2) to 9mL of ultrapure water were added 55mg of PVP, 65mg of ascorbic acid and 200mg of KCl at 90oStirring in C oil bath for 5min, adding 2mL of 3mmol/L Na2PdCl4The solution addition was continued at 90 deg.CoStirring for 2 hours in an oil bath, then alternately washing with acetone and ethanol, and dispersing in 12mL ethanol to obtain Pd colloid;
(3) dissolving ytterbium nitrate, lutetium nitrate, cerium nitrate and zirconium nitrate in 60mL of ethanol water solution, wherein the volume ratio of ethanol to water is 1:1, adding the Pd colloid in the step (2) into a beaker, adding an L-arginine solution, fully stirring for 2h at 90 ℃, washing for 5 times by using acetone, carrying out centrifugal separation, and dispersing in 12mL of ethanol to obtain a colloid (I); the molar ratio of ytterbium nitrate to lutetium nitrate to cerium nitrate to zirconium nitrate is as follows: 0.03:0.01:1: 1; the mass ratio of the Pd colloid to the L-arginine is 1: 2; the molar ratio of the Pd colloid to the cerium nitrate is 1: 0.6;
(4) adding the copper-modified alumina carrier in the step (1) into the colloid (I) in the step (3), stirring for 4h at room temperature, drying for 12h at 90 ℃ in a drying oven, roasting for 2h at 550 ℃ in a muffle furnace, and aging for 4h at 1100 ℃ in a mixed gas of water vapor and air, wherein the volume content of the water vapor is 12%, so as to prepare an aged three-way catalyst; wherein the loading of Pd was 0.08 wt%.
Example 3
A preparation method of a three-way catalyst for automobile exhaust comprises the following steps:
(1) soaking alumina particles with the diameter of 1.5mm in 50.0mL of mixed aqueous solution containing copper nitrate and urea, carrying out heat treatment at 60 ℃ for 24 hours, filtering, washing, drying at 100 ℃ for 12 hours, and roasting at 400 ℃ for 6 hours to obtain a copper-modified alumina carrier; the molar ratio of the aluminum oxide to the copper nitrate is 10: 1; the molar ratio of the urea to the copper nitrate is 6: 1;
(2) to 7mL of ultrapure water were added 45mg of PVP, 45mg of ascorbic acid and 55mg of KCl at 70oStirring in C oil bath for 20min, adding 4mL of 1 mmol/L Na2PdCl4Solution addition was continued at 70oStirring for 4 hours in an oil bath, then alternately washing with acetone and ethanol, and dispersing in 8mL of ethanol to obtain Pd colloid;
(3) dissolving ytterbium nitrate, lutetium nitrate, cerium nitrate and zirconium nitrate in 40mL of ethanol water solution, wherein the volume ratio of ethanol to water is 1:1, adding the Pd colloid in the step (2) into a beaker, adding an L-arginine solution, fully stirring for 4 hours at 70 ℃, washing for 3 times by using acetone, carrying out centrifugal separation, and dispersing in 8mL of ethanol to obtain colloid (I); the molar ratio of ytterbium nitrate to lutetium nitrate to cerium nitrate to zirconium nitrate is as follows: 0.01: 0.03:1: 1; the mass ratio of the Pd colloid to the L-arginine is 1: 1.5; the molar ratio of the Pd colloid to the cerium nitrate is 1: 0.4;
(4) adding the copper-modified alumina carrier in the step (1) into the colloid (I) in the step (3), stirring for 2h at room temperature, drying for 24h at 70 ℃ in an oven, then roasting for 4h at 450 to the temperature in a muffle furnace, and aging for 6h at 1000 ℃ in a mixed gas of water vapor and air, wherein the volume content of the water vapor is 8%, so as to prepare an aged three-way catalyst; wherein the loading of Pd was 0.01 wt%.
Comparative example 1
The copper modification was not performed, and other preparation processes and conditions were the same as in example 1.
Comparative example 2
Firstly, preparing ytterbium and lutetium modified cerium-zirconium solid solution, then loading the cerium-zirconium solid solution on the surface of copper modified alumina, and then impregnating Pd colloid to obtain the three-way catalyst, wherein the content and the proportion of raw materials involved in the preparation process are the same as those in example 1.
Comparative example 3
Only preparing ytterbium modified cerium-zirconium solid solution, wherein the molar ratio of ytterbium nitrate to cerium nitrate to zirconium nitrate is as follows: 0.04:1: 1; other preparation steps and conditions were the same as in example 1.
Comparative example 4
Only preparing lutetium modified cerium-zirconium solid solution, wherein the molar ratio of lutetium nitrate, cerium nitrate and zirconium nitrate is as follows: 0.04:1: 1; other preparation steps and conditions were the same as in example 1.
Comparative example 5
The ceria-zirconia solid solution was not subjected to ytterbium and lutetium modification, and other preparation steps and conditions were the same as in example 1.
Comparative example 6
The atmosphere during the aging treatment did not contain water vapor, and the other preparation processes and conditions were the same as in example 1.
Comparative example 7
(1) Soaking alumina particles with the diameter of 1.5mm in 50.0mL of copper nitrate-containing aqueous solution, carrying out heat treatment at 60 ℃ for 24 hours, filtering, washing, drying at 100 ℃ for 12 hours, and roasting at 400 ℃ for 6 hours to obtain a copper-loaded alumina carrier; the molar ratio of the aluminum oxide to the copper nitrate is 10: 1; the molar ratio of the urea to the copper nitrate is 6: 1;
steps (2) to (4) are the same as steps (2) to (4) in example 1.
The three-way catalysts of examples 1-3 and comparative examples 1-7 were used for automobile exhaust treatment. The specific method comprises the following steps:
using simulated automobile exhaust as reaction atmosphere, loading 200mg of catalyst with particle size of 50 meshes into a fixed bed reactor, wherein the automobile exhaust comprises 1.5% of CO and 0.25% of H2、500ppm HC(C3H8/C3H6=2:1)，1000ppm NO，1.5% O2，N2The reaction space velocity is 300 L.h for the balance gas-1·gcat -1Specific test results Table 1, wherein T is used50And T90Indicating the light-off temperature and the full conversion temperature.
TABLE 1T of three-way catalyst for CO, HC and NO50And T90Temperature of
As can be seen from the comparative examples of example 1 and comparative examples 1 to 7, the three-way catalyst of the present invention has excellent catalytic performance, has good removal capability for automobile exhaust, and is an ideal material for automobile exhaust treatment.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a three-way catalyst for automobile exhaust is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) soaking aluminum oxide particles with the diameter of 1.5mm in 50.0mL of mixed aqueous solution containing copper nitrate and urea, carrying out heat treatment at 60-90 ℃ for 12-24 hours, filtering, washing, drying, and roasting to obtain a copper-modified aluminum oxide carrier;
(2) adding PVP, ascorbic acid and KCl into ultrapure water, stirring for 5-20 min in an oil bath at 70-90 ℃, and adding 1-3 mmol/L Na2PdCl4Adding the solution, and continuously performing oil bath at 70-90 DEG CStirring for 2-4 h, then alternately washing with acetone and ethanol, and dispersing in ethanol to obtain Pd colloid;
(3) dissolving ytterbium nitrate, lutetium nitrate, cerium nitrate and zirconium nitrate in an ethanol water solution, adding the Pd colloid in the step (2) into a beaker, adding an L-arginine solution, fully stirring for 2-4 h at 70-90 ℃, washing for 3-5 times with acetone, carrying out centrifugal separation, and dispersing in ethanol to obtain a colloid (I);
(4) adding the copper-modified alumina carrier in the step (1) into the colloid (I) in the step (3), stirring for 2-4 h at room temperature, drying in an oven, roasting in a muffle furnace, and aging in a gas containing water vapor for 4-6 h at 1000-1100 ℃ to prepare an aged three-way catalyst; wherein the load of Pd is 0.01-0.08 wt%.
2. The method of claim 1, wherein: in the step (1), the molar ratio of the aluminum oxide to the copper nitrate is 10-20: 1; the molar ratio of the urea to the copper nitrate is 6-10: 1.
3. The method of claim 1, wherein: in the step (1), the drying is carried out for 6-12 hours at 100-130 ℃; the roasting is carried out at 400-500 ℃ for 2-6 hours.
4. The method of claim 1, wherein: in the step (2), the ultrapure water, PVP, ascorbic acid, KCl and Na2PdCl4The proportion of the solution is 7-9 mL: 45-55 mg; 55-65 mg; 185-200 mg: 2-4 mL; the volume of the ethanol is 8-12 mL.
5. The method of claim 1, wherein: in the step (3), the volume ratio of ethanol to water in the ethanol aqueous solution is 1: 1; the volume of the ethanol water is 40-60 mL; and after centrifugal separation, the volume of the used ethanol is 8-12 mL.
6. The method of claim 1, wherein: in the step (3), the molar ratio of ytterbium nitrate, lutetium nitrate, cerium nitrate and zirconium nitrate is as follows: 0.01-0.03: 1: 1; the mass ratio of the Pd colloid to the L-arginine is 1: 1.5-2; the mole ratio of the Pd colloid to the cerium nitrate is 1: 0.4-0.6.
7. The method of claim 1, wherein: in the step (4), the drying is carried out at 70-90 ℃ for 12-24 h; the roasting is carried out at the temperature of 450-550 ℃ for 2-4 h.
8. The method of claim 1, wherein: in the step (4), the gas containing water vapor is a mixed gas of water vapor and air, and the volume content of the water vapor is 8-12%.
9. A three-way catalyst for automobile exhaust prepared by the preparation method according to any one of claims 1 to 8.
10. The use of a three-way catalyst for automobile exhaust according to claim 9, wherein: the three-way catalyst is used for treating automobile exhaust, 150-250 mg of catalyst with the particle size of 40-60 meshes is loaded into a fixed bed reactor by taking simulated automobile exhaust as reaction atmosphere, and the automobile exhaust comprises 1.5-2% of CO and 0.2-0.3% of H2450 to 550ppm HC, wherein C3H8/C3H6＝2:1，900～1100ppm NO，1～2％O2，N2The reaction space velocity is 300 L.h for the balance gas-1·gcat -1。
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