CN101012767A - Automobile exhaust gas purifying installation with ceramic carrier supported catalyst and method for making same - Google Patents
Automobile exhaust gas purifying installation with ceramic carrier supported catalyst and method for making same Download PDFInfo
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- CN101012767A CN101012767A CNA2007100262837A CN200710026283A CN101012767A CN 101012767 A CN101012767 A CN 101012767A CN A2007100262837 A CNA2007100262837 A CN A2007100262837A CN 200710026283 A CN200710026283 A CN 200710026283A CN 101012767 A CN101012767 A CN 101012767A
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- Prior art keywords
- catalyst
- carrier
- mullite fiber
- ceramic
- exhaust gas
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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
Abstract
The invention provides a purifying device for automobile tail gas with ceramic carrier loaded catalyst and the manufacture method. The purifying device for automobile tail gas comprises ceramic carrier and catalyst on the carrier. The ceramic carrier is mullite fiber porous ceramic. The component of catalyst is ternary rare-earth perovskite salt composite oxidant, whose chemical formula is La1-XSrXCoO3 where X is 0.2-0.8. In preparing, at first, the carrier can be made by phosphoric acid, aluminum hydroxide and mullite fiber; then according to the chemical measuring ratio of catalyst, the nitrate solution with La, Sr and Co is collocated; and then the carrier is submerged in the catalyst solution; finally it is roasted. The prepared mullite fiber porous ceramic carrier is provided with high porosity (96% or so), high temperature resistance, smaller thermal expansion coefficient, good thermal shock resistance, easy control for the size of hole, the density of hole and the figure of hole so on. The carrier hole is 3-D stereo open-hole structure. The catalyst has very high conversion to CO and NO.
Description
Technical field
This patent relates to automobile exhaust gas purifying installation, particularly relates to automobile exhaust gas purifying installation of a kind of cellular ceramic substrate supported catalyst and preparation method thereof.
Background technique
Though being used for the cordierite carrier for ceramic honeycomb catalyst of purifying vehicle exhaust, to have a thermal shock resistance good, advantages such as air resistance is little, but also exist deficiency: 1. firing range is narrow, have only about 30 ℃, thereby sintering process is difficult to control, discharge with a large amount of constitution waters simultaneously, influential to intensity; 2. supported catalyst need additionally add Al
2O
3Coating increases specific surface area; 3. there are restraining factors in the mechanical property of the raising of honeycomb ceramic carrier porosity ratio and preparation process and carrier.Therefore be necessary to develop other novel practical ceramic monoliths, promote the development of China's catalytic cleaning of car tail gas research work.
For a long time, be that the catalyzer of main active component is considered to the most effective catalyzer of purifying automobile tail gas with the precious metal.But the precious metal resource scarcity, cost an arm and a leg, and because easy high temperature sintering of precious metal and volatilization make noble metal catalyst not preponderate aspect thermostability.People have the catalyzer that does not contain precious metal of high purification efficiency always in searching.Perofskite type oxide has lower price and flexible and changeable composition, and its catalytic performance can be regulated to a certain extent, thereby is subjected to people's attention.Replace as three-way catalyst with this compounds that traditional Pt/Rh is catalyst based to have a certain superiority.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, provide a kind of to CO and NO conversion ratio height, catalyst loadings is big, high temperature resistant, thermal expansion coefficient is less, thermal shock resistance is good, the size of hole, density, shape etc. are the automobile exhaust gas purifying installation of the cellular ceramic substrate supported catalyst of control easily.
Another object of the present invention is to provide the preparation method of the automobile exhaust gas purifying installation of above-mentioned ceramic carrier supported catalyst.
Purpose of the present invention is achieved through the following technical solutions.
A kind of automobile exhaust gas purifying installation of ceramic carrier supported catalyst, by ceramic monolith and load on supported catalyst and constitute, described ceramic monolith is the mullite fiber porous ceramics; Described catalyst activity component is a ternary RE perovskite salt composite oxidant, and its chemical formula is: La
1-xSr
xCoO
3, wherein X is 0.2～0.8, the weight of effective catalyst component is 10%～45% of mullite porous ceramic vehicle weight.
The preparation method of the automobile exhaust gas purifying installation of ceramic carrier supported catalyst comprises the steps and process conditions:
(1) preparing carriers: the forming method of mullite fiber porous ceramics is the pressurization fluid-discharge therapy.The A23 Bond of preparation is added deionized water by 1: 5～40 ratio to be diluted.Bond and mullite fiber that dilution is good mix, pour in the homemade shaping die, under the mould 200 purpose stainless steel mesh screens, above shaping die, feed suitable air pressure, unnecessary binder solution is discharged down from mesh screen, remove mould, like this with regard to forming the porous fiber ceramic base substrate.The base substrate of forming is put into about 120 ℃ baking oven, be about 5～30 hours time of drying; 1000 ℃～1300 ℃ roastings make the mullite fiber porous ceramics.
(2) configuration of catalyst solution: with La (NO
3)
3.6H
2O, Co (NO
3)
2.6H
2O, Sr (NO
3)
2Press chemical formula: La
1-XSr
XCoO
3The mole ratio of middle La, Sr, Co is hybridly prepared into the aqueous solution of 0.1～2mol/L nitrate, wherein: X=0.2～0.8.
(3) dipping: the mullite fiber porous ceramics of preparation is put into airtight container, pour the nitrate aqueous solution of excessive slightly above-mentioned La-Sr-Co into, vacuumize certain hour.Take out sample, 120 ℃ of dryings 12～24 hours.
(4) roasting: the porous ceramics after will flooding is put into stove, and 600～800 ℃ of roastings are 1～4 hour under inert gas atmosphere, obtain mullite fiber porous ceramics loaded catalyst.
With respect to prior art, the present invention has following advantage and beneficial effect:
(1) the mullite porous ceramic carrier porosity ratio height (about 96%) of the present invention preparation, high temperature resistant, thermal expansion coefficient is less, thermal shock resistance is good, the size of hole, density, shape etc. are control easily;
(2) the carrier hole of the present invention open-celled structure that is 3 D stereo.
(3) many ceramic monoliths forming method processing ease of the present invention practicality, equipment needed thereby are simple, and different moulds can obtain the difform carrier and the easily demoulding.
(4) catalyst loadings of the present invention is big, about about 45%.
(5) this catalyzer all has very high conversion to CO and NO, and below 400 ℃, the conversion ratio of NO is up to about 55%, and the CO conversion ratio is about 100%., more than 450 ℃, the conversion ratio of NO is about 70%, ranges up to 74.5%, the CO conversion ratio is about 99%.
Embodiment
The invention will be further described below in conjunction with embodiment; but be pointed out that following examples can not be interpreted as limiting the scope of the invention, those skilled in the art's foregoing according to the present invention still belongs to protection scope of the present invention to some nonessential improvement and the adjustment that the present invention makes.
Embodiment 1
Catalyst carrier is with phosphoric acid (H
3PO
4, analyze pure), aluminium hydroxide (Al (OH)
3, analyze pure) and mullite fiber (Al
2O
3+ SiO
2=98%) is raw material, phosphoric acid and aluminium hydroxide mixed with 23: 1 ratio of mol ratio that the preparation Bond adds deionized water with the Bond of preparation by 1: 15 ratio and dilutes.Bond and mullite fiber that dilution is good mix, and every 1000ml binder solution adding 75g mullite fiber is poured compression and moulding in the columniform shaping die into, 120 ℃ of dryings 12 hours; 1250 ℃ of insulations made the mullite fiber porous ceramics in 2 hours.With La (NO
3)
36H
2O, Co (NO
3)
26H
2O, Sr (NO
3)
2Press chemical formula: La
0.8Sr
0.2CoO
3The mixed in molar ratio of La, Co and each element of Sr is mixed with the aqueous solution of 1mol/L nitrate in the formula.The mullite fiber porous ceramics of preparation is put into airtight container, pour the nitrate aqueous solution of excessive slightly above-mentioned La-Sr-Co into, vacuumized 1 hour.Take out sample, 120 ℃ of dryings 12 hours.800 ℃ are incubated 1 hour, get the automobile exhaust gas purifying installation of ceramic carrier supported catalyst.Ceramic monolith porosity ratio height, high temperature resistant, thermal expansion coefficient is less, thermal shock resistance is good, and hole is the open-celled structure of 3 D stereo; During high temperature, the conversion ratio of NO is up to 74.5%, and this moment, the CO conversion ratio was about 99%.
Embodiment 2
Catalyst carrier is with phosphoric acid (H
3PO
4, analyze pure), aluminium hydroxide (Al (OH)
3, analyze pure) and mullite fiber (Al
2O
3+ SiO
2=98%) is raw material, earlier phosphoric acid and aluminium hydroxide mixed with 23: 1 ratio of mol ratio that the preparation Bond adds deionized water with the Bond of preparation by 1: 40 ratio and dilutes.Bond and mullite fiber that dilution is good mix, and every 1000ml binder solution adds 60 mullite fibers and pours compression and moulding in the moulding cylindrical die into, 120 ℃ of dryings 5 hours; 1300 ℃ of insulations made the mullite fiber porous ceramics in 2 hours.With La (NO
3)
36H
2O, Co (NO
3)
26H
2O, Sr (NO
3)
2Press chemical formula: La
0.2Sr
0.8CoO
3The mixed in molar ratio of middle La, Co and each element of Sr is mixed with the aqueous solution of 2mol/L nitrate.The mullite fiber porous ceramics of preparation is put into airtight container, pour the nitrate aqueous solution of excessive slightly above-mentioned La-Sr-Co into, vacuumized 1 hour.Take out sample, 110 ℃ of dryings 20 hours, 700 ℃ of insulations 2 hours obtain the automobile exhaust gas purifying installation of ceramic carrier supported catalyst.Ceramic monolith porosity ratio height (relatively embodiment's 1 height), high temperature resistant, thermal expansion coefficient is less, thermal shock resistance is good, and hole is the open-celled structure of 3 D stereo; During high temperature, the conversion ratio of NO and CO is better.
Embodiment 3
Catalyst carrier is with phosphoric acid (H
3PO
4, analyze pure), aluminium hydroxide (Al (OH)
3, analyze pure) and mullite fiber (Al
2O
3+ SiO
2=98%) is raw material, earlier phosphoric acid and aluminium hydroxide mixed with 23: 1 ratio of mol ratio that the preparation Bond adds deionized water with the Bond of preparation by 1: 5 ratio and dilutes.Bond and mullite fiber that dilution is good mix, and every 1000ml binder solution adding 100g mullite fiber is poured compression and moulding in the cylindrical shaping die into, 100 ℃ of dryings 30 hours; 1000 ℃ of insulations made the mullite fiber porous ceramics in 2 hours.With La (NO
3)
36H
2O, Co (NO
3)
26H
2O, Sr (NO
3)
2Press chemical formula: La
0.8Sr
0.2CoO
3The mixed in molar ratio of middle La, Co and each element of Sr is mixed with the aqueous solution of 0.1mol/L nitrate.The mullite fiber porous ceramics of preparation is put into airtight container, pour the nitrate aqueous solution of excessive slightly above-mentioned La-Sr-Co into, vacuumized 1 hour.Take out sample, 100 ℃ of dryings 24 hours.600 ℃ are incubated 4 hours, obtain the automobile exhaust gas purifying installation of ceramic carrier supported catalyst.Ceramic monolith porosity ratio height (relatively embodiment 1 low), high temperature resistant, thermal expansion coefficient is less, thermal shock resistance is good, and hole is the open-celled structure of 3 D stereo; During high temperature, the conversion ratio of NO and CO is better.
Embodiment 4
Catalyst carrier is with phosphoric acid (H
3PO
4, analyze pure), aluminium hydroxide (Al (OH)
3, analyze pure) and mullite fiber (Al
2O
3+ SiO
2=98%) is raw material, phosphoric acid and aluminium hydroxide mixed with 23: 1 ratio of mol ratio that the preparation Bond adds deionized water with the Bond of preparation by 1: 15 ratio and dilutes.Bond and mullite fiber that dilution is good mix, and every 1000ml binder solution adds 50 mullite fibers and pours compression and moulding in the cylindrical shaping die into, 120 ℃ of dryings 12 hours; 1250 ℃ of insulations made the mullite fiber porous ceramics in 2 hours.With La (NO
3)
36H
2O, Co (NO
3)
26H
2O, Sr (NO
3)
2, PdCl
2Press chemical formula: La
0.6Sr
0.4Co
0.9Pd
0.1O
3The mixed in molar ratio of middle La, Co and each element of Sr is mixed with the aqueous solution of 1mol/L nitrate.The mullite fiber porous ceramics of preparation is put into airtight container, pour the nitrate aqueous solution of excessive slightly above-mentioned La-Sr-Co into, vacuumized 1 hour.Take out sample, 120 ℃ of dryings 12 hours, 800 ℃ of insulations 2 hours, the automobile exhaust gas purifying installation of ceramic carrier supported catalyst.A small amount of Pd joins La
0.8Sr
0.2CoO
3Effect has clearly not only reduced the activity of such catalysts temperature, and has improved catalytic efficiency greatly in the catalyzer, and especially the reduction reaction effect to NO is obvious.
Claims (3)
1, a kind of automobile exhaust gas purifying installation of ceramic carrier supported catalyst, by ceramic monolith and load on supported catalyst and constitute, it is characterized in that: described ceramic monolith is the mullite fiber porous ceramics; Described catalyst activity component is a ternary RE perovskite salt composite oxidant, and its chemical formula is: La
1-XSr
XCoO
3, wherein: X is 0.2～0.8, the weight of described effective catalyst component is 10%～45% of mullite porous ceramic vehicle weight.
2, the preparation method of the automobile exhaust gas purifying installation of the described ceramic carrier supported catalyst of claim 1 is characterized in that comprising the steps and process conditions:
(1) preparing carriers: with excessive phosphoric acid and Al (OH)
3Reaction makes Bond; Then Bond is added the deionized water dilution in 1: 5～40 ratio, again mullite fiber is added in the binder solution, every 1000ml binder solution adds 50～100g mullite fiber, stir, mix, pour the shaping die moulding into and make base substrate, it is 100～120 ℃ baking oven that base substrate is put into temperature, 5～30 hours time of drying; Roasting makes the mullite fiber porous ceramics under 1000 ℃～1300 ℃ temperature conditions;
(2) configuration of catalyst solution: by the catalyst chemical formula is La
1-XSr
XCoO
3Stoichiometric proportion, configuration concentration is La, the Sr of 0.1～2mol/L, the nitrate aqueous solution of Co, wherein X is 0.2～0.8;
(3) dipping: the carrier of step (1) preparation is put into airtight container, pour La, Sr, the Co nitrate aqueous solution of excessive slightly step (2) configuration into, vacuumize, take out sample, 100 ℃～120 ℃ dryings 12～24 hours;
(4) roasting: the roasting 1～4 hour under inert gas atmosphere and 600 ℃～800 ℃ temperature conditions of the porous ceramics after will flooding, the automobile exhaust gas purifying installation of ceramic carrier supported catalyst.
3, the preparation method of the automobile exhaust gas purifying installation of ceramic carrier supported catalyst according to claim 2 is characterized in that the nitrate aqueous solution of described step (2) configuration La, Co and Sr is with La (NO
3)
3.6H
2O, Co (NO
3)
2.6H
2O and Sr (NO
3)
2Press chemical formula La
1-XSr
XCoO
3The mole ratio of middle La, Co and Sr is mixed the aqueous solution of joining nitrate; Described X is 0.2～0.8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100262837A CN101012767A (en) | 2007-01-12 | 2007-01-12 | Automobile exhaust gas purifying installation with ceramic carrier supported catalyst and method for making same |
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|---|---|---|---|
| CNA2007100262837A CN101012767A (en) | 2007-01-12 | 2007-01-12 | Automobile exhaust gas purifying installation with ceramic carrier supported catalyst and method for making same |
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| Publication Number | Publication Date |
|---|---|
| CN101012767A true CN101012767A (en) | 2007-08-08 |
Family
ID=38700473
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|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284215B (en) * | 2008-06-03 | 2011-06-15 | 华南理工大学 | Preparation method of perovskite hollow fiber membrane |
| CN105110779A (en) * | 2015-01-02 | 2015-12-02 | 海南大学 | Preparation method of mullite porous ceramic by welding whisker |
| CN106166491A (en) * | 2016-07-22 | 2016-11-30 | 武汉理工大学 | A kind of mesoporous La0.8sr0.2coO3load nano Ce O2catalyst and its preparation method and application |
| CN109437959A (en) * | 2018-12-20 | 2019-03-08 | 东北大学 | A kind of method that environment-friendly type gel injection-moulding prepares mullite fiber base porous ceramics |
| CN112108512A (en) * | 2020-09-07 | 2020-12-22 | 生态环境部南京环境科学研究所 | Organic contaminated soil remediation device and method based on regenerative tail gas desorption auxiliary agent |
| CN112128781A (en) * | 2020-09-23 | 2020-12-25 | 苏州云式环境科技有限公司 | Organic waste gas recovery processing system |
| CN112121581A (en) * | 2020-09-23 | 2020-12-25 | 苏州云式环境科技有限公司 | Industrial tail gas treatment system |
| CN113943169A (en) * | 2020-07-16 | 2022-01-18 | 南京航空航天大学 | SiC nanowire reinforced oxide ceramic matrix composite and preparation method thereof |
-
2007
- 2007-01-12 CN CNA2007100262837A patent/CN101012767A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101284215B (en) * | 2008-06-03 | 2011-06-15 | 华南理工大学 | Preparation method of perovskite hollow fiber membrane |
| CN105110779A (en) * | 2015-01-02 | 2015-12-02 | 海南大学 | Preparation method of mullite porous ceramic by welding whisker |
| CN106166491A (en) * | 2016-07-22 | 2016-11-30 | 武汉理工大学 | A kind of mesoporous La0.8sr0.2coO3load nano Ce O2catalyst and its preparation method and application |
| CN106166491B (en) * | 2016-07-22 | 2019-01-25 | 武汉理工大学 | A kind of mesoporous La0.8Sr0.2CoO3Load nano Ce O2Catalyst and its preparation method and application |
| CN109437959A (en) * | 2018-12-20 | 2019-03-08 | 东北大学 | A kind of method that environment-friendly type gel injection-moulding prepares mullite fiber base porous ceramics |
| CN109437959B (en) * | 2018-12-20 | 2021-06-11 | 东北大学 | Method for preparing mullite fiber-based porous ceramic by using environment-friendly gel casting |
| CN113943169A (en) * | 2020-07-16 | 2022-01-18 | 南京航空航天大学 | SiC nanowire reinforced oxide ceramic matrix composite and preparation method thereof |
| CN112108512A (en) * | 2020-09-07 | 2020-12-22 | 生态环境部南京环境科学研究所 | Organic contaminated soil remediation device and method based on regenerative tail gas desorption auxiliary agent |
| CN112128781A (en) * | 2020-09-23 | 2020-12-25 | 苏州云式环境科技有限公司 | Organic waste gas recovery processing system |
| CN112121581A (en) * | 2020-09-23 | 2020-12-25 | 苏州云式环境科技有限公司 | Industrial tail gas treatment system |
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