CN106362764B - A kind of cleaning catalyst for tail gases of automobiles and preparation method thereof - Google Patents
A kind of cleaning catalyst for tail gases of automobiles and preparation method thereof Download PDFInfo
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- CN106362764B CN106362764B CN201610785858.2A CN201610785858A CN106362764B CN 106362764 B CN106362764 B CN 106362764B CN 201610785858 A CN201610785858 A CN 201610785858A CN 106362764 B CN106362764 B CN 106362764B
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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
- 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
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
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- 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
- B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
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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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- 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
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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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Abstract
The present invention provides a kind of cleaning catalyst for tail gases of automobiles, can reduce the use of noble metal, and improve catalytic activity, which is characterized in that the ReM of the laminated perovskite structure comprising Ag doping2(Cu, Co, Mn)3‑δAgδO7, wherein Re is rare earth element, and M is alkali earth metal, 0≤δ≤0.5.The present invention also provides the preparation methods of the catalyst, comprising: 1) stoichiometrically weighs the nitrate of each metallic element and be dissolved in water, citric acid or glycine and ethylene glycol is added；2) it microwave heating and stirs, until gel state is presented；3) heat drying, grinding, obtains brown precursor；4) it is calcined under 600~800 DEG C, air atmosphere, forms final catalyst.
Description
[technical field]
The present invention relates to field of exhaust gas purification more particularly to a kind of cleaning catalyst for tail gases of automobiles and preparation method thereof.
[background technique]
Vehicle tail gas reforming catalyst is studied, the discharge for controlling automobile exhaust pollutant is extremely urgent, to this
The research in field becomes a global project.
The catalyst of the direction is mainly with Pt Pt-Ru or Pt-Pd-Ru noble metal triple effect catalysis as main component at present
Agent, preparation method mostly use multiple maceration, representative patents such as CN1342520A, CN1385239A, CN1413769A,
CN1502410A, CN1511621A etc..Although such catalyst activity is high, preparation process is complicated, at high cost, in the item of high temperature
Sintering deactivation easily occurs under part.It is rare-earth composite oxide catalyst there are also one kind, such as La-K-Mn-O catalyst (Applied
Catalysis B:34 (2001) 73-78), the maximum conversion of NO is less than 35% at 400 DEG C；CoFe2O4Catalyst
(Catalysistoday:119 (2007) 267-272), the maximum conversion of NO is less than 30%；K modified La2CuO4Catalyst
(Catalysistoday:119 (2007) 267-272), the maximum conversion of NO is less than 30%；Cu modified La2NiO4Catalyst
(Catal Lett (2009) 132:41-49), the maximum conversion of NO is less than 20%.This kind of catalyst avoids making for noble metal
With, but comparatively activity is not high, is not suitable for purifying vehicle exhaust.
[summary of the invention]
The object of the present invention is to provide a kind of cleaning catalyst for tail gases of automobiles, can reduce the use of noble metal, and
Improve catalytic activity.
Another object of the present invention, which also resides in, provides the preparation method of above-mentioned cleaning catalyst for tail gases of automobiles, can obtain expensive
The cleaning catalyst for tail gases of automobiles that tenor is few, catalytic activity is high.
The technical scheme is that
A kind of cleaning catalyst for tail gases of automobiles, which is characterized in that the ReM of the laminated perovskite structure comprising Ag doping2
(Cu, Co, Mn)3-δAgδO7, wherein Re is rare earth element, and M is alkali earth metal, 0≤δ≤0.5.Above-mentioned ReM2(Cu, Co,
Mn)3-δAgδO7, be three layers of perovskite structure of part Ag doping, belong to rhombic system, wherein rare earth ion and 8 oxygen from
Son coordination, alkaline-earth metal ions and 10 oxonium ions are coordinated, and there are two types of different lattice positions for transition metal ions.As doping Ag+
Into after in lattice, higher-priced transition metal ion content can be made to increase, enhance oxidability, and form fault of construction,
The mobility for promoting Lattice Oxygen enhances Redox ability, to improve the activity of catalyst.
Further, above-mentioned rare earth element Re is one or more of La, Ce, Y.
Further, above-mentioned alkali earth metal M is one or more of Ba, Sr.
Further, the doping δ of above-mentioned silver is 0.05≤δ≤0.1.
Another technical solution of the invention are as follows:
A kind of preparation method of above-mentioned cleaning catalyst for tail gases of automobiles, which is characterized in that comprise the steps of:
1) it stoichiometrically weighs the nitrate of each metallic element and is dissolved in water, citric acid or glycine and second two is added
Alcohol forms mixed solution；
2) it by the mixed solution microwave heating of step 1) and stirs, until gel state is presented；
3) the gel heat drying for obtaining step 2), then grinds, and obtains brown precursor；
4) the brown precursor that step 3) obtains is calcined under 600~800 DEG C, air atmosphere, forms final catalysis
Agent.
Further, above-mentioned steps 1) in the additional amount of citric acid or glycine be total metal ion 0.8~
1.2 times, citric acid or glycine both make complexing agent, also make reducing agent.
Further, above-mentioned steps 1) in the additional amount of ethylene glycol be 0.5~1 times of aqueous solution volume, ethylene glycol plus
Enter to be conducive to product and forms uniform small particles.
Further, above-mentioned steps 2) in microwave power be 300~600W.
Further, above-mentioned steps 3) in grind product particle size be more than or equal to 3000 mesh.
Further, above-mentioned steps 4) in the product calcined be white powder, the terminal of calcining forms perovskite with product
Subject to structure, the apparent phenomenon is white powder, and the structure of formation is more complete, and product is more stable, and catalytic effect is more permanent.
The invention has the following beneficial technical effects:
1) the activation site of catalyst of the invention is transition metal ions, adulterates Ag+Be introduced into and can make in structure high price
The transition metal ion content of position increases, and enhances reducing power, and form fault of construction, promotes the mobility of Lattice Oxygen,
Redox ability is enhanced, to improve the activity of catalyst, the temperature that carbon monoxide (CO) converts completely correspondingly declines,
Hydrocarbon (HC) and oxynitride (NOx) conversion ratio correspondingly improve；2) catalyst of the invention is by Ag+Into lattice
Structure keeps the structure of catalyst more stable, and thermal stability is more preferable；3) catalyst and preparation method thereof of the invention only used
Few noble metal (Ag), greatly reduces the dosage of noble metal, and reach the catalytic effect being close with noble metal catalyst,
It reduces costs, improves efficiency.
[specific embodiment]
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment provided below is not the range that is covered to limit the utility model, and described step is not yet
It is to execute sequence to limit its.Those skilled in the art combine existing common knowledge to do conspicuous improvement to the present invention,
Also fall into the present invention claims protection scope within.
Embodiment one
A kind of cleaning catalyst for tail gases of automobiles, active constituent are the laminated perovskite structure of Ag doping, and chemical formula is
LaBa2Cu2Mn0.5Ag0.5O7, belong to rhombic system, wherein rare earth ion and 8 oxonium ions are coordinated, alkaline-earth metal ions with
10 oxonium ion coordinations, there are two types of different lattice positions for transition metal ions.As doping Ag+Into after in lattice, high price can be made
The transition metal ion content of position increases, and enhances oxidability, and form fault of construction, promotes the mobility of Lattice Oxygen,
Redox ability is enhanced, to improve the activity of catalyst.
The preparation method of above-mentioned cleaning catalyst for tail gases of automobiles comprises the steps of:
1) it stoichiometrically weighs the nitrate of each metallic element and is dissolved in water, total metal ion is added
0.8~1.2 times of citric acid or glycine, and 0.5~1 times of ethylene glycol of aqueous solution volume is added, form mixed solution；
2) mixed solution of step 1) using 300~600W microwave heating and is stirred, until gel state is presented；
3) the gel heat drying for obtaining step 2), then grinds, and takes the brown precursor of 3000 mesh or more；
4) the brown precursor for obtaining step 3) is calcined under 600~800 DEG C, air atmosphere until forming white powder
Perovskite structure forms final catalyst.
Above-mentioned catalyst is coated on honeycomb metal skeleton, the temperature that the CO in vehicle exhaust is converted completely from
250 DEG C of NO when correspondingly dropping to 190 DEG C, 400 DEG CxMaximum conversion be 92%, HC maximum conversion be 89%.
Embodiment two
A kind of cleaning catalyst for tail gases of automobiles, active constituent are the laminated perovskite structure of Ag doping, and chemical formula is
La0.7Ce0.3Sr2Co2Mn0.9Ag0.1O7, belong to rhombic system, wherein rare earth ion and 8 oxonium ions are coordinated, alkaline-earth metal
Ion and 10 oxonium ions are coordinated, and there are two types of different lattice positions for transition metal ions.As doping Ag+Into after in lattice, meeting
Increase higher-priced transition metal ion content, enhances oxidability, and form fault of construction, promote the work of Lattice Oxygen
Dynamic degree, enhances Redox ability, to improve the activity of catalyst.
The preparation method of above-mentioned cleaning catalyst for tail gases of automobiles comprises the steps of:
1) it stoichiometrically weighs the nitrate of each metallic element and is dissolved in water, total metal ion is added
0.8~1.2 times of citric acid or glycine, and 0.5~1 times of ethylene glycol of aqueous solution volume is added, form mixed solution；
2) mixed solution of step 1) using 300~600W microwave heating and is stirred, until gel state is presented；
3) the gel heat drying for obtaining step 2), then grinds, and takes the brown precursor of 3000 mesh or more；
4) the brown precursor for obtaining step 3) is calcined under 600~800 DEG C, air atmosphere until forming white powder
Perovskite structure forms final catalyst.
Above-mentioned catalyst is coated on honeycomb metal skeleton, the temperature that the CO in vehicle exhaust is converted completely from
250 DEG C of NO when correspondingly dropping to 196 DEG C, 400 DEG CxMaximum conversion be 87%, HC maximum conversion be 79%.
Embodiment three
A kind of cleaning catalyst for tail gases of automobiles, active constituent are the laminated perovskite structure of Ag doping, and chemical formula is
La0.7Y0.3Ba1.5Sr0.3Co2Mn0.95Ag0.05O7, belong to rhombic system, wherein rare earth ion and 8 oxonium ions are coordinated, alkali
Earthmetal cations and 10 oxonium ions are coordinated, and there are two types of different lattice positions for transition metal ions.As doping Ag+Into in lattice
Afterwards, higher-priced transition metal ion content can be made to increase, oxidability is enhanced, and form fault of construction, promote lattice
The mobility of oxygen enhances Redox ability, to improve the activity of catalyst.
The preparation method of above-mentioned cleaning catalyst for tail gases of automobiles comprises the steps of:
1) it stoichiometrically weighs the nitrate of each metallic element and is dissolved in water, total metal ion is added
0.8~1.2 times of citric acid or glycine, and 0.5~1 times of ethylene glycol of aqueous solution volume is added, form mixed solution；
2) mixed solution of step 1) using 300~600W microwave heating and is stirred, until gel state is presented；
3) the gel heat drying for obtaining step 2), then grinds, and takes the brown precursor of 3000 mesh or more；
4) the brown precursor for obtaining step 3) is calcined under 600~800 DEG C, air atmosphere until forming white powder
Perovskite structure forms final catalyst.
Above-mentioned catalyst is coated on honeycomb metal skeleton, the temperature that the CO in vehicle exhaust is converted completely from
250 DEG C of NO when correspondingly dropping to 195 DEG C, 400 DEG CxMaximum conversion be 88%, HC maximum conversion be 81%.
Claims (6)
1. a kind of preparation method of cleaning catalyst for tail gases of automobiles, which is characterized in that cleaning catalyst for tail gases of automobiles is mixed comprising silver
The ReM of miscellaneous laminated perovskite structure2(Cu, Co, Mn)3-δAgδO7, wherein Re is rare earth element, and M is alkali earth metal；
The rare earth element Re is one or more of La, Ce, Y；
The alkali earth metal M is one or more of Ba, Sr；
The doping δ of the silver is 0.05≤δ≤0.1；
The preparation method of the cleaning catalyst for tail gases of automobiles comprising the steps of:
1) it stoichiometrically weighs the nitrate of each metallic element and is dissolved in water, citric acid or glycine and ethylene glycol is added,
Form mixed solution；
2) it by the mixed solution microwave heating of step 1) and stirs, until gel state is presented；
3) the gel heat drying for obtaining step 2, then grinds, and obtains brown precursor；
4) the brown precursor that step 3) obtains is calcined under 600-800 DEG C, air atmosphere, forms final catalyst.
2. the preparation method of cleaning catalyst for tail gases of automobiles according to claim 1, which is characterized in that in the step 1)
The additional amount of citric acid or glycine is 0.8-1.2 times of total metal ion.
3. the preparation method of cleaning catalyst for tail gases of automobiles according to claim 1, which is characterized in that in the step 1)
The additional amount of ethylene glycol is 0.5-1 times of aqueous solution volume.
4. the preparation method of cleaning catalyst for tail gases of automobiles according to claim 1, which is characterized in that in the step 2
Microwave power is 300-600W.
5. the preparation method of cleaning catalyst for tail gases of automobiles according to claim 1, which is characterized in that in the step 3)
The product particle size of grinding is more than or equal to 3000 mesh.
6. the preparation method of cleaning catalyst for tail gases of automobiles according to claim 1, which is characterized in that in the step 4)
The product of calcining is white powder.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1618944A1 (en) * | 2004-07-23 | 2006-01-25 | Dowa Mining Co., Ltd. | Perovskite complex oxide and exhaust gas purification catalyst |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1618944A1 (en) * | 2004-07-23 | 2006-01-25 | Dowa Mining Co., Ltd. | Perovskite complex oxide and exhaust gas purification catalyst |
| CN1724147A (en) * | 2004-07-23 | 2006-01-25 | 同和矿业株式会社 | Perovskite complex oxide and catalyst |
Non-Patent Citations (1)
| Title |
|---|
| corrosion behavior of high-temperature superconductor YBa2Cu3-YAgyO7-x in the presence of water;Young-Soon Kim等;《Korean J of Chem. Eng.》;19951231;第12卷(第5期);第563-566页 |
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