CN106732578B - A kind of mesoporous cerium zirconium aluminum composite oxides carried noble metal nanocatalyst of efficient cryogenic, preparation method and applications - Google Patents
A kind of mesoporous cerium zirconium aluminum composite oxides carried noble metal nanocatalyst of efficient cryogenic, preparation method and applications Download PDFInfo
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- CN106732578B CN106732578B CN201611001940.8A CN201611001940A CN106732578B CN 106732578 B CN106732578 B CN 106732578B CN 201611001940 A CN201611001940 A CN 201611001940A CN 106732578 B CN106732578 B CN 106732578B
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- cerium zirconium
- composite oxides
- aluminum composite
- noble metal
- zirconium aluminum
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- 239000002131 composite material Substances 0.000 title claims abstract description 59
- -1 cerium zirconium aluminum Chemical compound 0.000 title claims abstract description 52
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 21
- 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 37
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- 239000004411 aluminium Substances 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 14
- 229910052763 palladium Inorganic materials 0.000 claims description 12
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- SWCIQHXIXUMHKA-UHFFFAOYSA-N aluminum;trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SWCIQHXIXUMHKA-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- CQGVSILDZJUINE-UHFFFAOYSA-N cerium;hydrate Chemical compound O.[Ce] CQGVSILDZJUINE-UHFFFAOYSA-N 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000013067 intermediate product Substances 0.000 claims description 4
- 239000002082 metal nanoparticle Substances 0.000 claims description 4
- 238000007747 plating Methods 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- ATYZRBBOXUWECY-UHFFFAOYSA-N zirconium;hydrate Chemical compound O.[Zr] ATYZRBBOXUWECY-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 239000006193 liquid solution Substances 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- 239000011148 porous material Substances 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 25
- 239000001301 oxygen Substances 0.000 abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 abstract description 25
- 238000003860 storage Methods 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 25
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001802 infusion Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011232 storage material Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—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
-
- B01J35/393—
-
- B01J35/613—
-
- B01J35/64—
-
- 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
Abstract
A kind of negative noble metal nano catalyst of the mesoporous cerium zirconium aluminium of low temperature high catalytic activity, preparation method and applications, belong to catalyst technical field.A certain amount of noble metal is loaded on three-dimensional ordered mesoporous cerium zirconium aluminum composite oxides hole wall.Preparation method is to prepare mesoporous cerium zirconium alumina supporter using negative pressure method, and noble-metal-supported is then obtained the nanocatalyst of mesoporous cerium zirconium aluminium carried noble metal in mesoporous cerium zirconium aluminium surface using equi-volume impregnating.CO concentration is 1.6%, HC concentration is 0.05%, NOx concentration 0.1%, O2Concentration is 1.0%, H2Concentration is 0.23%, N2Balance, air speed 300, under the conditions of 000mL/ (g h), which has a biggish specific surface area, and in higher storage oxygen, the catalyst is with transformation efficiency with higher at a lower temperature.Raw material of the present invention is cheap and easy to get, and preparation process is simple, and product morphology and aperture are controllable, and catalytic performance is excellent.
Description
Technical field
The present invention relates to a kind of three-dimensional ordered mesoporous cerium zirconium aluminum composite oxides carried noble metal nanocatalyst, the present invention
The preparation method for further relating to prepare this three-dimensional ordered mesoporous cerium zirconium aluminum composite oxides carrier, relates in particular to negative pressure legal system
Standby cerium zirconium aluminum composite oxides carrier, the application the invention further relates to this nanocatalyst in purifying vehicle exhaust field belong to
In catalyst technical field.
Background technique
Motor vehicle exhaust emission has become one of most important pollution sources in the large size cities such as Beijing, Shanghai and Guangzhou, for this purpose, state
Auto emission standard is continuously improved in family.Gasoline car three-way catalyst is by the noble metal active components such as Pt, Rh, Pd, cerium base
Hydrogen-storing material and the γ-Al for being used to support active component2O3Carrier composition.Hydrogen-storing material is to the dispersion of noble metal and has stablized pass
Key effect, can improve noble metal high high-temp stability and oxygen storage capacity, expand its air-fuel ratio operation window, stablize γ-
Al2O3The specific surface area of carrier prevents γ-Al2O3Phase transition caused by due to sintering and raising carrier γ-Al2O3High warm
Stability.Performance of the physical and chemical performances such as oxygen storage capacity, redox property and the specific surface area of hydrogen-storing material to three-way catalyst
There is larger impact.
Cerium-based oxygen storage material is widely studied and applies, and the application in three-way catalyst experienced three phases: the
One stage was CeO2Application, but at 850 DEG C or more, CeO2It is easy to happen high temperature sintering, only Surface Oxygen participates in catalysis reaction,
Lead to catalyst inactivation.Second stage is by ZrO2Mix CeO2In, cerium zirconium sosoloid is formed, CeO can be effectively inhibited2Oxygen is stored up in sintering
Ability is significantly improved with thermal stability, but still is unable to satisfy increasingly strict auto emission standard.Phase III is
The application of ternary cerium base oxide uses noble metal, transition metal, rare earth metal and Al2O3It is mixed Deng to cerium zirconium sosoloid modification
It is miscellaneous, further increase the oxygen storage capacity and hydrothermal stability of cerium-based oxygen storage material.
The Chinese invention patent application of Publication No. CN1200954A discloses one kind and infusion process is taken to prepare cerium-based oxygen storage
The method of material is loaded to cerium oxide and ceria stabilized agent on the aluminium oxide of high-specific surface area by infusion process, 900 DEG C
It is made within roasting 10 hours.Prepared cerium-based oxygen storage material specific surface area is up to 30m2/ g or so.From X-ray diffraction spectrogram
Observe CeO2And Al2O3Characteristic diffraction peak, which is not directed to the Oxygen storage capacity of prepared hydrogen-storing material.Chinese invention is special
Sharp CN101112683A discloses an one-step preparation method of cerium zirconium aluminum composite oxides, joined surfactant before precipitating, filter
It is roasted after cake drying, simple process, but the specific surface area of products therefrom is lower, high-temperature stability is poor.Patent
CN102886526A discloses a kind of Cerium zirconium aluminum composite oxide oxygen storage material and preparation method thereof, although obtaining after fresh and aging
Kong Rong greatly and specific surface area are obtained, but also without the related data of related oxygen storage capacity.Have document report (Zhao Ming, Chen Yao are strong etc.,
CeO2-ZrO2-AL2O3Preparation and its load palladium three-way catalyst catalytic [J] .Chin.J.Catal, 2010,31:429-
434), palladium-based catalyst made from the cerium zirconium aluminum composite oxides carrier and infusion process using coprecipitation preparation, although having
Biggish specific surface area and higher oxygen storage capacity, but its three-way catalytic activity need to be improved.The sample of coprecipitation preparation
With large specific surface area, but its cellular structure is but the unordered cellular structure that particle packing is formed, and it is living to be unfavorable for noble metal
The high degree of dispersion of property component, while being also unfavorable for the diffusion of reactants and products molecule, catalytic activity is to be improved.Therefore,
It researches and develops three-dimensional ordered mesoporous hydrogen-storing material of the one kind both with high-specific surface area, high Oxygen storage capacity and is used as auto-exhaust catalyst
Carrier is of great significance for the raising of three-way catalyst performance.
Precious metals pt, Rh, Pd are the active components of orthodox car three-way catalyst, and Pd has CO, HC and nitrogen oxides
There is preferable catalytic action, especially the price of Pd is lower with respect to Pt, Rh in noble metal, and present invention is generally directed to three-dimensional ordered mesoporous
Cerium zirconium aluminum composite oxides load the expansion of Pd nanocatalyst.
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of three-dimensional ordered mesoporous cerium zirconium aluminum composite oxides and its loading your gold
Belong to the preparation method of nanocatalyst, this method simple process, controllable, suitable large-scale production.Gained cerium zirconium aluminum composite oxide
The well-regulated three-dimensional ordered mesoporous structure of object tool, higher specific surface area, excellent oxygen storage capacity and high high-temp stability, 1000
That Al is not precipitated after DEG C aging 5h2O3Phase is still uniform cerium based solid solution structure, noble metal component height in gained catalyst
Dispersion.The present invention also provides application of this nanocatalyst in catalytic cleaning of car tail gas field, the nanocatalysts
With excellent three-way catalytic performance.
Three-dimensional ordered mesoporous cerium zirconium aluminum composite oxides carried noble metal nanocatalyst, which is characterized in that there is three-dimensional
Load has a certain amount of noble metal nano particles on the hole wall of the cerium zirconium aluminum composite oxides of ordered mesopore structure, and wherein noble metal is received
The load capacity of rice grain is 0-3wt%.The molar ratio of cerium zirconium is 1-1.5:1, and preferably cerium zirconium molar ratio is 6:4,
The mass percentage 0-80% of aluminium oxide in cerium zirconium aluminum composite oxides;It is preferred that oxygen in cerium zirconium aluminum composite oxides
The mass percentage for changing aluminium is 40%.
A kind of preparing of the present invention as three-dimensional ordered mesoporous cerium zirconium aluminum composite oxides carried noble metal nanocatalyst
Method, wherein the aperture of cerium zirconium aluminum composite oxides is 2-10nm, and fresh specific surface area is 100-250m2/ g, 1000 DEG C, 5h is old
Specific surface area is 50-90m after change2/ g (is shown in Table 2).
Three-dimensional ordered mesoporous cerium zirconium aluminum composite oxides carried noble metal nanocatalyst is prepared the present invention provides a kind of
Method, which comprises the following steps:
(1) three-dimensional ordered mesoporous cerium zirconium aluminum composite oxides carrier is prepared, a certain amount of KIT-6 powder is weighed, is placed in dry
It in dry bottle,suction, vacuumizes, bottle,suction is always under negative pressure state in whole preparation process;In addition stoichiometric ratio is weighed
Six nitric hydrate cerium (Ce (NO3)3·6H2O), five nitric hydrate zirconium (Zr (NO3)3·5H2) and ANN aluminium nitrate nonahydrate (Al O
(NO3)3·9H2O it) is placed in a beaker, dehydrated alcohol is added thereto, it is compound that three kinds of nitrate obtain cerium zirconium aluminium after being completely dissolved
The precursor solution of oxide, and be transferred in separatory funnel;Under condition of negative pressure, separatory funnel cock is opened, forerunner is made
Liquid solution is slowly dropped in KIT-6 powder, and after being added dropwise, continuation filters under condition of negative pressure, until without more in bottle,suction
Extraction raffinate body obtains the compound of KIT-6 and presoma;It is roasted after object to be composite is dry, roasting condition is as follows: in Muffle furnace
In with the rate of 1 DEG C/min rise to 550 DEG C by room temperature, keep the temperature 3h, Temperature fall obtains light yellow solid;With hot NaOH solution concentration
(2mol/L) removes KIT-6 template, obtains mesoporous cerium zirconium aluminum composite oxides carrier after washing, drying;
(2) mesoporous supports obtained by step (1) are weighed to be put into container for use, weigh a certain amount of precious metal soluble salt plating
Liquid (bullion content is 15wt% in such as plating solution), is added deionized water dilution, is then put into dilution and fills mesoporous supports
Beaker in;Container is put into 60 DEG C of ultrasound 3h in Vltrasonic device and is put into Muffle kiln roasting after solvent volatilizees completely, is roasted
Burning condition is raised to 500 DEG C from room temperature for 1 DEG C/min, keeps the temperature 3h, obtains mesoporous cerium zirconium aluminum composite oxides carried noble metal catalysis
Agent.
Vacuumized in preferred steps (1) so that vacuum degree be 0.7-1Mpa, be added precursor solution before the pumpdown time extremely
Few 1h.
It is preferred that the drop rate of precursor solution is 10-50 drop/min, every drop about 0.2ml.Hot NaOH's is dense in step (1)
Degree is 2mol/L, every 1g mesoporous supports hot NaOH solution of 100ml.
It is preferred that vacuum impregnation technology is used to be prepared for cerium zirconium molar ratio as 6:4, the mass fraction of aluminium oxide is the load of 0-80%
Body, wherein cerium zirconium has more regular meso-hole structure, higher than the composite oxides for being 40wt% for 6:4, alumina content
Specific surface area and biggish oxygen storage capacity, therefore select the cerium zirconium aluminum composite oxides of this ratio as carrier.Using infusion process
It is multiple to get three-dimensional ordered mesoporous cerium zirconium aluminium the noble metal (preferably 1-2.0wt%) of different quality containing has been loaded respectively on it
Close oxide carried noble metal nano catalyst.
Above-mentioned noble metal is selected from Pt, Rh, Pd, preferably Pd.
The present invention relates to three-dimensional ordered mesoporous cerium zirconium aluminum composite oxides carried noble metal nanocatalysts in vehicle exhaust
Application in catalytic purification field.
The present invention has raw material cheap and easy to get, and preparation process is simple, and it is special that products therefrom pattern, partial size and aperture are controllable etc.
Sign.
Three-dimensional ordered mesoporous carrier specific surface area prepared by the present invention is high, oxygen storage capacity is big, and using it as the palladium chtalyst of carrier
Agent, to CO, CH, NOx while conversion ratio with higher, has good in lower temperature in catalytic cleaning of car tail gas field
Application prospect.
Utilize D8ADVANCE type X-ray diffractometer (XRD), JEOL-2010 type transmission electron microscope (TEM) and FEI
Crystal structure, particle morphology, particle structure and the hole of target product obtained by the instrumental characterizings such as G2 80-200/Chem-STEM are tied
Structure.The result shows that being according to mesoporous cerium zirconium aluminum composite oxides carried noble metal nanocatalyst obtained by the method for the present invention
Existing excellent three-way catalytic performance.
Detailed description of the invention
Fig. 1 is that (cerium zirconium ratio is 6:4, aoxidizes mesoporous cerium zirconium aluminum composite oxides carrier obtained by embodiment 2
Aluminium content is 40wt%) small angle XRD spectra.
Fig. 2 is that (cerium zirconium ratio is 6:4, oxygen to mesoporous cerium zirconium aluminum composite oxides carrier obtained by embodiment 2-4
Changing aluminium content is 20,40,60wt%) carrier is fresh and the wide-angle XRD spectra of aged samples.
Fig. 3 is mesoporous cerium zirconium aluminum composite oxides carrier composite oxide carrier (cerium obtained by embodiment 2
Zirconium ratio is 6:4, aluminium oxygen content is 40wt%) TEM picture.
Fig. 4 is that (cerium zirconium ratio is 6:4 to obtained cerium zirconium aluminum composite oxides composite oxide carrier, aluminium oxygen content is
40wt%) the catalytic activity curve of supported palladium (load capacity of Pd is 1%, 2%) nanocatalyst, reaction gas composition are as follows: CO
Concentration 1.6%, HC concentration are 0.05% (molar concentration rate of propane and propylene is 1:3), NOx concentration 0.1%, O2Concentration is
1.0%, H2Concentration is 0.23%, N2For Balance Air, air speed 300,000mL/ (gh).
Specific embodiment
It is only intended to that the present invention will be described in detail below with reference to embodiment, does not limit the protection model of invention in any way
It encloses.It vacuumizes so that vacuum degree is 0.7-1Mpa, the pumpdown time is at least 1h before precursor solution is added.
Embodiment 1:
The preparation of three-dimensional ordered mesoporous cerium zirconium sosoloid: it takes the KIT-6 powder of 2g to be placed in dry bottle,suction, vacuumizes
1.5 hour;It weighs six nitric hydrate cerium of 5.96g and five nitric hydrate zirconium of 7.35g is placed in a beaker, it is anhydrous that 40ml is added thereto
Ethyl alcohol obtains precursor solution until completely dissolved, acquired solution is transferred in separatory funnel;Liquid separation leakage is opened under condition of negative pressure
Struggle against cock, be slowly dropped to precursor solution in KIT-6 powder, after being added dropwise, continuation kept under same vacuum degree to
Without surplus liquid in bottle,suction, the compound of KIT-6 template and precursor solution is obtained, it is obtained in Muffle kiln roasting
The compound of KIT-6 template and cerium zirconium sosoloid, roasting condition are as follows: with the rate of 1 DEG C/min by room temperature to 550 DEG C, protect
Warm 3h, is down to room temperature naturally;KIT-6 template is removed with the hot NaOH solution of 2mol/L, washing, drying obtain three-dimensional order Jie
Hole cerium zirconium sosoloid.
Embodiment 2:
The preparation of three-dimensional ordered mesoporous cerium zirconium aluminum composite oxides (alumina content 20wt%): 2g KIT-6 powder is weighed
End is placed in dry bottle,suction, is vacuumized 1 hour;Weigh six nitric hydrate cerium of 5.96g, five nitric hydrate zirconium of 7.35g and
3.33g ANN aluminium nitrate nonahydrate 80ml dehydrated alcohol is added thereto, acquired solution is transferred to separatory funnel until completely dissolved
In;Experimental procedure later is same as Example 1, and final obtains three-dimensional ordered mesoporous cerium zirconium aluminum composite oxides, wherein oxygen
The content for changing aluminium is 20wt%.
Embodiment 3:
The preparation of three-dimensional ordered mesoporous cerium zirconium aluminum composite oxides (alumina content 40wt%): the experiment of embodiment 3
Step is same as Example 2, and only the amount of precursor salt is different from embodiment 2.Six nitric hydrate ceriums are in the present embodiment
5.96g, five nitric hydrate zirconiums are 7.35g, ANN aluminium nitrate nonahydrate 8.87g, gained three-dimensional ordered mesoporous cerium zirconium aluminum composite oxide
The content of aluminium oxide is 40wt% in object.Sample has apparent diffraction maximum in little Jiao Chu as can be seen from Figure 1, illustrates have in sample
Meso-hole structure exists.It can be seen that the sample forms good three-dimensional ordered mesoporous structure from Fig. 3 transmission electron microscope.
Embodiment 4:
The preparation of three-dimensional ordered mesoporous cerium zirconium aluminum composite oxides (alumina content 60wt%): the experiment of embodiment 4
Step is identical as embodiment 2 and 3, and only the amount of precursor salt is different from embodiment 2 and 3.Six nitric hydrate cerium in the present embodiment
For 5.96g, five nitric hydrate zirconiums are 7.35g, ANN aluminium nitrate nonahydrate 16.98g, gained three-dimensional ordered mesoporous cerium zirconium aluminium composite oxygen
The content of aluminium oxide is 60wt% in compound.The peak intensity after it can be seen that fresh sample aging obtained by embodiment 2-4 in Fig. 2 XRD
There is not Al without significant change in degree enhancing, peak width2O3Characteristic peak, illustrate that sample forms the cerium zirconium aluminium of stable homogeneous
Solid solution.
Embodiment 5:
Load capacity is the preparation of the mesoporous cerium zirconium aluminum composite oxides supported palladium nanocatalyst of 1wt%: by embodiment 3
Step prepares mesoporous supports (alumina content 40wt%), weighs 2g carrier and is put into the small beaker of 25ml;Weigh 0.134g
Nitric acid palladium plating solution (mass fraction 15%) move into putting in the beaker of carrier, will burn after the dilution of 5ml deionized water is added
Cup is put into ultrasonic cleaner, after 60 DEG C of ultrasound 3h, intermediate product is put into Muffle kiln roasting, roasting condition: with 1
DEG C/rate of min from room temperature is raised to 500 DEG C, 3h is kept the temperature, it is negative to obtain the mesoporous cerium zirconium aluminum composite oxides that load capacity is 1wt%
Carry palladium nanocatalyst.
Embodiment 6:
Load capacity be 2wt% mesoporous cerium zirconium aluminum composite oxides supported palladium nanocatalyst preparation: the embodiment with
The preparation step of embodiment 5 is identical, only palladium nitrate used cross liquid amount it is different, palladium nitrate crosses the dosage of liquid and is in the embodiment
0.268g, the load capacity of Pd is 2wt% in gained catalyst.Embodiment 5 and 6 is related to catalyst at 200 DEG C as can be seen from Figure 4
Higher conversion was attained by three kinds of pollutants in the past, shows excellent catalytic activity.
The oxygen storage capacity and the specific surface before and after aging that wherein above-described embodiment is related to mesoporous cerium zirconium aluminum composite oxides carrier
Integral is not shown in Tables 1 and 2.From the data in the table, sample has excellent oxygen storage capacity and higher specific surface area.
Table 1 is the oxygen storage capacity of the mesoporous cerium zirconium aluminum composite oxides of obtained different alumina contents
Table 2 is the specific surface area before and after the obtained mesoporous cerium zirconium aluminum composite oxides aging of different alumina contents
Claims (8)
1. a kind of preparation method of three-dimensional ordered mesoporous cerium zirconium aluminum composite oxides carried noble metal nanocatalyst, feature exist
In, three-dimensional ordered mesoporous cerium zirconium aluminum composite oxides carried noble metal nanocatalyst, the cerium with three-dimensional ordered mesoporous structure
Load has a certain amount of noble metal nano particles on the hole wall of zirconia-alumina composite oxide;Wherein the load capacity of noble metal nano particles is
0-3wt%;The molar ratio of cerium zirconium is 1-1.5:1, the mass percentage 0-80% of aluminium oxide in cerium zirconium aluminum composite oxides;
Specific preparation method the following steps are included:
(1) three-dimensional ordered mesoporous cerium zirconium alumina supporter is prepared, takes a certain amount of KIT-6 powder to be placed in dry bottle,suction and vacuumizes
For a period of time, it takes six nitric hydrate ceriums, five nitric hydrate zirconiums and ANN aluminium nitrate nonahydrate to be added in dehydrated alcohol, is dissolved to solid
Afterwards, above-mentioned precursor solution is put into separatory funnel, bottle,suction opens always separatory funnel cock under evacuated state
It is slowly dropped to precursor solution in KIT-6 powder, after being added dropwise, continues to keep the nothing into bottle,suction under the vacuum degree
Obvious surplus liquid just obtains intermediate product, roasting condition are as follows: with 1 DEG C/min speed by room temperature to 540 in Muffle furnace
DEG C, and 3h is kept, then being down to room temperature naturally obtains light yellow solid;It is washed in removal light yellow solid with the hot NaOH of 2mol/L
After KIT-6 template, mesoporous cerium zirconium aluminum composite oxides carrier is obtained after washing is dry;
(2) it weighs a certain amount of mesoporous cerium zirconium aluminum composite oxides carrier to be put into container for use, weighs a certain amount of noble metal
Soluble-salt plating solution is added deionized water dilution, is then put into dilution and fills mesoporous cerium zirconium aluminum composite oxides carrier
In container;Container is put into 60 DEG C of ultrasound 3h in Vltrasonic device and obtains intermediate product, intermediate product is put into Muffle kiln roasting,
Roasting condition is that 1 DEG C/min is raised to 500 DEG C from room temperature and keeps the temperature 3h, then obtains your gold mesoporous cerium zirconium aluminum composite oxides load
The catalyst of category.
2. according to method of claim 1, which is characterized in that vacuumized in step (1) so that vacuum degree is 0.7-1Mpa, addition
The pumpdown time is 1-1.5h before precursor solution.
3. according to method of claim 1, which is characterized in that the drop rate of precursor solution is 20-40 drop/min.
4. according to method of claim 1, which is characterized in that the concentration of hot NaOH is 2mol/L, every 1g carrier pair in step (1)
100ml solution is answered, removal KIT-6 need to be cleaned every time.
5. according to method of claim 1, which is characterized in that cerium zirconium molar ratio is 6:4, aluminium oxide in cerium zirconium aluminum composite oxides
Mass percentage be 40%.
6. according to method of claim 1, which is characterized in that the load capacity of noble metal nano particles is 1-2wt%.
7. according to method of claim 1, which is characterized in that noble metal is selected from Pt, Rh, Pd.
8. a kind of preparation method of three-dimensional ordered mesoporous cerium zirconium aluminum composite oxides carrier, which is characterized in that weigh a certain amount of
KIT-6 powder is placed in dry bottle,suction, vacuumizes, and bottle,suction is always under negative pressure state in whole preparation process;In addition
Weigh six nitric hydrate cerium (Ce (NO3)3·6H2O), five nitric hydrate zirconium (Zr (NO3)3·5H2) and ANN aluminium nitrate nonahydrate (Al O
(NO3)3·9H2O it) is placed in a beaker, dehydrated alcohol is added thereto, it is compound that three kinds of nitrate obtain cerium zirconium aluminium after being completely dissolved
The precursor solution of oxide, and be transferred in separatory funnel;Under condition of negative pressure, separatory funnel cock is opened, forerunner is made
Liquid solution is slowly dropped in KIT-6 powder, and after being added dropwise, continuation filters under condition of negative pressure, until without more in bottle,suction
Extraction raffinate body obtains the compound of KIT-6 and presoma;It is roasted after object to be composite is dry, roasting condition is as follows: in Muffle furnace
In with the rate of 1 DEG C/min rise to 550 DEG C by room temperature, keep the temperature 3h, Temperature fall obtains light yellow solid;It is removed with hot NaOH solution
KIT-6 template obtains mesoporous cerium zirconium aluminum composite oxides carrier after washing, drying;The molar ratio of cerium zirconium is 1-1.5:1,
The mass percentage 0-80% of aluminium oxide in cerium zirconium aluminum composite oxides;
The mesoporous pore size of the cerium zirconium aluminum composite oxides of three-dimensional ordered mesoporous structure is 2nm-10nm, and fresh specific surface area is
100m2/g-250m2/ g, 1000 DEG C, specific surface area is 50m after 5h aging2/ g~90m2/g。
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