CN103920485A - Modified active alumina material for motor vehicle tail gas purification - Google Patents
Modified active alumina material for motor vehicle tail gas purification Download PDFInfo
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- CN103920485A CN103920485A CN201310726294.1A CN201310726294A CN103920485A CN 103920485 A CN103920485 A CN 103920485A CN 201310726294 A CN201310726294 A CN 201310726294A CN 103920485 A CN103920485 A CN 103920485A
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- temperature
- stove
- aluminum oxide
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Abstract
A modified active alumina material for motor vehicle tail gas purification is characterized in that the general formula of the modified active alumina material is MxAlyO2, wherein M can be Ce, Zr, La, Ba, Y or/and Co, or can also be a mixture comprising two or above two of Ce, Zr, La, Ba, Y and Co; and x is greater than 0.1 and lower than 0.3, y is greater than 0.7 and lower than 0.9, x+y=1, and x and y represent the percentage proportions of elements in the total mass of the material respectively. The modification element(s) in MxAlyO2 can delay the phase transition process of active alumina, and has/have a very good texture stability, a very good structure stability and a certain oxygen storage amount, so the ageing resistance of the material is improved, and the implementation of a catalytic reaction is promoted.
Description
Technical field
The present invention is specifically related to motor vehicle tail-gas purifying modified activated aluminum oxide material.
Background technology
At present, develop rapidly along with national economy, the quantity of China's automobile rapidly increases, by the end of 2012 the end of the year China's automobile recoverable amount reached 1.2 hundred million, the whole people of automobile popularize and make national trip become more and more convenient, but the pollution problem that meanwhile vehicle exhaust produces environment is also more and more serious.Three-way catalyst is to control CO, HC and NO in vehicle exhaust
xeffective means, and activated alumina is the core material in ternary catalyzing unit.
Activated alumina has that specific area is high, crystalline phase temperature range is wide, pore structure is adjustable, surface has the advantages such as acid, can increase the decentralization of active component during as catalyst carrier, improves catalytic reaction activity.But in actual purifying vehicle exhaust process; three-way catalyst is arranged on engine export place conventionally; under high temperature and the simultaneous reaction environment of steam; easily there is sintering and phase transformation in activated alumina; to α phase stable on thermodynamics and bulky grainization, change; specific area is significantly declined, cause that the decentralization of active component reduces, cause whole catalysqt deactivation.
Summary of the invention
Object of the present invention is exactly for above-mentioned deficiency, and a kind of motor vehicle tail-gas purifying modified activated aluminum oxide material is provided.
The general formula of modified activated aluminum oxide material of the present invention is M
xal
yo
2, wherein M is Ce, Zr, La, Ba, Y or/and Co element, or M is that in Ce, Zr, La, Ba, Y and Co element, any two kinds of elements or two or more element mix arbitrarily; 0.1<x<0.3,0.7<y<0.9, and x+y=1, wherein x, y represent that element in material accounts for the percentage of this material gross mass.
Concrete preparation method is as follows:
The configuration of a, salting liquid
According to modified activated aluminum oxide M
xal
yo
2concrete constituent and the content of middle M, calculate the corresponding nitrate content of the oxide content adding in M, and take corresponding nitrate, after nitrate is joined in container and adding deionized water and stirring to solid to dissolve completely, make salting liquid standby, dissolving required temperature range is 0-80 ℃;
The configuration of b, dispersion soln
Ratio according to polyethylene glycol and deionized water 2:4-6 is dissolved in polyethylene glycol in deionized water uniformly, makes dispersion soln;
C, stirring pulping
The salting liquid configuring in step a is joined in beaker, and by modified activated aluminum oxide M
xal
yo
2in the required low silicon boehmite of macropore and high sticky boehmite according to weight ratio 1:0.8-1.2, after evenly mixing, join in same beaker, under the condition of stirring in water bath, temperature is 75-85 ℃, and then the speed with 120-170r/min starts to stir, and adds salpeter solution acidifying form slurry shape in whipping process, pH value is controlled between 2.5-3.5, continues to stir 25-35min after form slurry;
D, ageing
Dispersion soln is added in slurry, bath temperature is increased to 92-97 ℃, keep the mixing speed of 120-170r/min, be incubated after 6-12 hour and stop heating, naturally cool to room temperature, make ageing slurry;
E, spraying are dried
Utilize spray drying device that ageing slurry is sprayed dry, dried powder granularity is controlled between 15-25 μ m, makes dried material;
F, M
xal
yo
2preparation
Dried material is put into Muffle furnace, according to following program, carries out roasting:
First temperature in stove is warming up to 115-125 ℃, insulation
0.9-1.1h;
then temperature in stove is warming up to 280-320 ℃,insulation
0.9-1.1h;
again temperature in stove is warming up to 330-370 ℃,insulation
1.3-1.7h;
again temperature in stove is warming up to 680-720 ℃,insulation
1.3-1.7h;
finally temperature in stove is warming up to 880-920 ℃,insulation
2.8-3.2h.
Then cooling coming out of the stove, after above-mentioned calcination procedure, obtains required modified activated aluminum oxide M
xal
yo
2.
Advantage of the present invention is: M
xal
yo
2in modifying element can postpone the phase transition process of activated alumina, make activated alumina under more than 1000 ℃ conditions, still can keep у-Al
2o
3activated state, there is good texture stability and structural stability, and possess certain oxygen storage capacity, not only can improve the ageing resistace of material, can also promote the carrying out of catalytic reaction.The present invention can also be for the feature of different automotive emissions, by element choose and arrange in pairs or groups after cooperative effect, targetedly to the pollutant of too high levels in exhaust emissions (CO NO
xhC) carry out reinforced purification.The economic environmental protection of preparation method of the present invention, is suitable for suitability for industrialized production.
The specific embodiment
The general formula of modified activated aluminum oxide material of the present invention is M
xal
yo
2, wherein M is Ce, Zr, La, Ba, Y or/and Co element, or M is that in Ce, Zr, La, Ba, Y and Co element, any two kinds of elements or two or more element mix arbitrarily; 0.1<x<0.3,0.7<y<0.9, and x+y=1, wherein x, y represent that element in material accounts for the percentage of this material gross mass.
Concrete preparation method is as follows:
The configuration of a, salting liquid
According to modified activated aluminum oxide M
xal
yo
2concrete constituent and the content of middle M, calculate the corresponding nitrate content of the oxide content adding in M, and take corresponding nitrate, after nitrate is joined in container and adding deionized water and stirring to solid to dissolve completely, make salting liquid standby, dissolving required temperature range is 50 ℃;
The configuration of b, dispersion soln
Ratio according to polyethylene glycol and deionized water 2:5 is dissolved in polyethylene glycol in deionized water uniformly, makes dispersion soln;
C, stirring pulping
The salting liquid configuring in step a is joined in beaker, and by modified activated aluminum oxide M
xal
yo
2in the required low silicon boehmite of macropore and high sticky boehmite according to weight ratio 1:1, after evenly mixing, join in same beaker, under the condition of stirring in water bath, temperature is 80 ℃, and then the speed with 150r/min starts to stir, and adds salpeter solution acidifying form slurry shape in whipping process, pH value is controlled between 3, continues to stir 30min after form slurry;
D, ageing
Dispersion soln is added in slurry, bath temperature is increased to 95 ℃, keep the mixing speed of 150r/min, be incubated after 8 hours and stop heating, naturally cool to room temperature, make ageing slurry;
E, spraying are dried
Utilize spray drying device that ageing slurry is sprayed dry, dried powder granularity is controlled between 20 μ m, makes dried material;
F, M
xal
yo
2preparation
Dried material is put into Muffle furnace, according to following program, carries out roasting:
First temperature in stove is warming up to 120 ℃,
1h;
then temperature in stove is warming up to 300 ℃, 1h;
again temperature in stove is warming up to 450 ℃, 1.5h;
again temperature in stove is warming up to 600 ℃, 1.5h;
finally temperature in stove is warming up to 900 ℃, 3h.
Then cooling coming out of the stove, after above-mentioned calcination procedure, obtains required modified activated aluminum oxide M
xal
yo
2.
Above-mentioned said M
xal
yo
2the texture property of modified activated aluminum oxide adopts Build SSA-4200 surface analysis instrument to measure, and first application of vacuum 1 hour at 350 ℃ of sample, take N2 as adsorbate, measures above-mentioned said M under liquid nitrogen temperature (196 ℃)
xal
yo
2the structural stability of modified activated aluminum oxide is analyzed on the German Bruker D8 ADVANCE of company type XRD analysis instrument.The K alpha ray of Cu target is radiation source, 40kV scanning voltage, 40mA sweep current, °-80 ° of scope interscans in 2 θ=10, above-mentioned said M
xal
yo
2the oxygen storage capacity of modified activated aluminum oxide (OSC) adopts oxygen Pulse adsorption technology to measure on homemade mobile micro-reaction equipment.Equipment chief component comprises: external gas cylinder, gas circuit, six-way valve, temperature programmed control system, electric furnace, detection system, data acquisition logging system.Wherein measuring system is the GC9790 type gas chromatograph with TCD detector.Take 0.80g particle diameter sample between 30-40 order and be placed in U-shaped Guan Zhonghou and put into electric furnace, connect gas circuit, at high-purity H
2atmosphere (flow velocity is 30ml/min) Program heats up, and by room temperature, rises to 550 ℃, keeps H
2the constant constant temperature reduction of speed 45min, uses high-purity N instead
2atmosphere (flow velocity is 30ml/min) purges sample and is cooled to 200 ℃.Connect GC, after baseline stability, by six-way valve, carry out O
2air-flow (flow velocity is 30ml/min) pulse, detects O
2absorbing state.
Claims (2)
1. motor vehicle tail-gas purifying modified activated aluminum oxide material, the general formula that it is characterized in that modified activated aluminum oxide material is M
xal
yo
2, wherein M is Ce, Zr, La, Ba, Y or/and Co element, or M is that in Ce, Zr, La, Ba, Y and Co element, any two kinds of elements or two or more element mix arbitrarily; 0.1<x<0.3,0.7<y<0.9, and x+y=1, wherein x, y represent that element in material accounts for the percentage of this material gross mass.
2. motor vehicle tail-gas purifying according to claim 1 modified activated aluminum oxide material, is characterized in that concrete preparation method is as follows:
The configuration of a, salting liquid
According to modified activated aluminum oxide M
xal
yo
2concrete constituent and the content of middle M, calculate the corresponding nitrate content of the oxide content adding in M, and take corresponding nitrate, after nitrate is joined in container and adding deionized water and stirring to solid to dissolve completely, make salting liquid standby, dissolving required temperature range is 0-80 ℃;
The configuration of b, dispersion soln
Ratio according to polyethylene glycol and deionized water 2:4-6 is dissolved in polyethylene glycol in deionized water uniformly, makes dispersion soln;
C, stirring pulping
The salting liquid configuring in step a is joined in beaker, and by modified activated aluminum oxide M
xal
yo
2in the required low silicon boehmite of macropore and high sticky boehmite according to weight ratio 1:0.8-1.2, after evenly mixing, join in same beaker, under the condition of stirring in water bath, temperature is 75-85 ℃, and then the speed with 120-170r/min starts to stir, and adds salpeter solution acidifying form slurry shape in whipping process, pH value is controlled between 2.5-3.5, continues to stir 25-35min after form slurry;
D, ageing
Dispersion soln is added in slurry, bath temperature is increased to 92-97 ℃, keep the mixing speed of 120-170r/min, be incubated after 6-12 hour and stop heating, naturally cool to room temperature, make ageing slurry;
E, spraying are dried
Utilize spray drying device that ageing slurry is sprayed dry, dried powder granularity is controlled between 15-25 μ m, makes dried material;
F, M
xal
yo
2preparation
Dried material is put into Muffle furnace, according to following program, carries out roasting:
First temperature in stove is warming up to 115-125 ℃, insulation
0.9-1.1h;
then temperature in stove is warming up to 280-320 ℃,insulation
0.9-1.1h;
again temperature in stove is warming up to 330-370 ℃,insulation
1.3-1.7h;
again temperature in stove is warming up to 680-720 ℃,insulation
1.3-1.7h;
finally temperature in stove is warming up to 880-920 ℃,insulation
2.8-3.2h;
Then cooling coming out of the stove, after above-mentioned calcination procedure, obtains required modified activated aluminum oxide M
xal
yo
2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310726294.1A CN103920485A (en) | 2013-12-26 | 2013-12-26 | Modified active alumina material for motor vehicle tail gas purification |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310726294.1A CN103920485A (en) | 2013-12-26 | 2013-12-26 | Modified active alumina material for motor vehicle tail gas purification |
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|---|---|
| CN103920485A true CN103920485A (en) | 2014-07-16 |
Family
ID=51139018
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1096716A (en) * | 1993-06-24 | 1994-12-28 | 中国石油化工总公司抚顺石油化工研究院 | A kind of method for preparing alumina support |
| US20070179054A1 (en) * | 2006-02-02 | 2007-08-02 | Mazda Motor Corporation | Exhaust gas purification catalyst |
| CN101239309A (en) * | 2008-02-22 | 2008-08-13 | 江苏金长江环保汽摩消声器有限公司 | High specific area cerium aluminium base composite oxides and preparation thereof |
| CN103406116A (en) * | 2013-07-23 | 2013-11-27 | 上海华明高纳稀土新材料有限公司 | High heat-resistant modified aluminum oxide and preparation method thereof |
-
2013
- 2013-12-26 CN CN201310726294.1A patent/CN103920485A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1096716A (en) * | 1993-06-24 | 1994-12-28 | 中国石油化工总公司抚顺石油化工研究院 | A kind of method for preparing alumina support |
| US20070179054A1 (en) * | 2006-02-02 | 2007-08-02 | Mazda Motor Corporation | Exhaust gas purification catalyst |
| CN101239309A (en) * | 2008-02-22 | 2008-08-13 | 江苏金长江环保汽摩消声器有限公司 | High specific area cerium aluminium base composite oxides and preparation thereof |
| CN103406116A (en) * | 2013-07-23 | 2013-11-27 | 上海华明高纳稀土新材料有限公司 | High heat-resistant modified aluminum oxide and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 宋为聪，等: ""YSZ-Al2O3的制备及其负载的单钯密偶催化剂的催化性能"", 《无机化学学报》, vol. 25, no. 5, 31 May 2009 (2009-05-31) * |
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Application publication date: 20140716 |