CN102728382A - Catalytic complex for denitration of lean burn gasoline engine exhaust and preparation method thereof - Google Patents
Catalytic complex for denitration of lean burn gasoline engine exhaust and preparation method thereof Download PDFInfo
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- CN102728382A CN102728382A CN2011100918382A CN201110091838A CN102728382A CN 102728382 A CN102728382 A CN 102728382A CN 2011100918382 A CN2011100918382 A CN 2011100918382A CN 201110091838 A CN201110091838 A CN 201110091838A CN 102728382 A CN102728382 A CN 102728382A
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- copper
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- titanium dioxide
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Abstract
A catalytic complex for denitration of lean burn gasoline engine exhaust and a preparation method thereof aim to overcome unsuitability of an existing ternary composite catalyst catalytic complex for lean burn technology. The catalytic complex comprises a cellular titanium dioxide carrier and metal platinum, rare earth metal, and metal copper that are attached to the carrier. The preparation method includes steps of: immersing titanium dioxide into a copper sulfate pentahydrate solution with a concentration of 75%, and drying and roasting to obtain a copper/ titanium dioxide catalyst complex; immersing the copper/ titanium dioxide catalyst complex in a rare earth cerium solution, and then drying and roasting to obtain a cerium / copper / titanium dioxide catalyst complex; and immersing the cerium / copper / titanium dioxide catalyst into a platinum nitrate salt solution, and drying and roasting to obtain a nitrate platinum / cerium / copper / titanium dioxide catalyst complex. The invention is beneficial to nitrogen oxides and reduction thereof, and significantly reduces temperature of harmless transformation of nitrogen oxides, and improves the ability of resistance to sulfur poisoning of the catalyst. Besides, the catalytic complex reduces use amount of noble metal platinum and cost of catalyst, and conducts efficient reduction on NOx in lean burn of gasoline engine exhaust.
Description
Technical field:
The invention belongs to vehicular field, be specifically related to automobile exhaust purifier
Background technology:
Because human dependence to automobile further strengthens, the quantity of automobile presents explosive growth.Nitrogen oxide in the automobile engine tail gas can be discharged among the atmosphere in a large number, the nitrogen oxide (NO in the vehicle exhaust
x) be atmosphere major pollution thing, nitrogen oxide not only can damage the mankind's respiratory system, and the arch-criminal of problems such as photochemical pollution, city ash haze weather, atmospheric acid sedimentation.For petrol engine,, basically all installed ternary composite catalyzing device additional in order to reduce exhaust emission standard.Ternary composite catalyzing device in the past can purify CO, HC compound and NO preferably under the operating mode of theoretical air-fuel ratio (14.7)
x, but along with the development of achieving lean combustion in engine such as stratified combustion technology (strengthening the mixed proportion of air and fuel oil), contain a large amount of O of burning of participating in the motor exhaust
2, the CO that exists in the tail gas, reducing substances such as HC are CO by dioxygen oxidation
2And H
2O, the minimizing of reducing substances just causes nitrogen oxide can not all be reduced to harmless N
2And H
2O.In order to reach the purpose of thorough purifying nitrogen oxide, adopt the method (SCR) of in gas extraction system, adding reducing agent (ammonia or urea) at present, but this method exists reducing agent to add difficulty and is prone to cause secondary pollution problem.In addition, the catalyst that existing compound three-way catalyst uses is a noble metal (Pt/Rh/Pd) etc., these metals not only cost an arm and a leg and also anti-sulphur property poor.
Summary of the invention:
The purpose of this invention is to provide a kind of lean-burn gasoline motor exhaust denitrating catalyst complex and preparation method; Overcome existing ternary composite catalyzing device catalytic composite and be inappropriate for lean burn technology, cause reducing agent interpolation difficulty and be prone to cause deficiencies such as secondary pollution problem and use noble metals such as (Pt/Rh/Pd) do not cost an arm and a leg, anti-sulphur property difference.
The catalyst composite of invention is by cellular titanium white powder (TiO
2) carrier and form attached to the metal platinum on the carrier (Pt), rare earth metal cerium (Ce) and metallic copper (Cu), the parts by weight ratio of each raw material consumption of catalyst is: metal platinum (Pt) 4-8 weight portion, rare earth metal cerium (Ce) 30-90 weight portion, metallic copper (Cu) 80-130 weight portion.
The preparation method of catalyst composite comprises the steps: among the present invention
1, with titanium white powder (TiO
2) be in 75% the 5 brochanite solution for the honeycomb support of base material immerses concentration; Under 18-25 ℃ of condition, keep 3-5 hour time; Put into drying baker then and carry out 12-15 hour oven dry 85-110 ℃ of scope; Carrier after the oven dry is gone into Muffle furnace in 500-800 ℃ of scope, carry out 5-7 hour roasting, obtain copper/titanium white powder (Cu/TiO
2) catalyst composite;
2, will form copper/titanium white powder (Cu/TiO through step 1
2) catalyst composite immerses in the rare earth cerium solution that concentration is 45-55% and soaked 5-7 hour under 18-25 ℃ of condition, the cerium salt that is adopted here is meant cerous acetate (Ce (CH
3COO)
3).Put into drying baker then and carry out 12-15 hour oven dry, the carrier after the oven dry is gone into Muffle furnace in 500-800 ℃ of scope, carry out 5-7 hour roasting, form cerium/copper/titanium white powder (Ce/Cu/TiO 85-110 ℃ of scope
2) catalyst composite;
3, it is in the platinum nitrate salting liquid of 55-75% that the cerium/copper that step 2 is obtained/titanium white powder catalyst composite immerses concentration; Soaked 3-5 hour under the 18-25 ℃ of condition; Put into drying baker then and carry out 12-15 hour oven dry 85-110 ℃ of scope; Carrier after the oven dry is gone into Muffle furnace in 500-800 ℃ of scope, carry out 5-7 hour roasting, promptly make lean-burn gasoline motor exhaust denitration platinum/cerium/copper/titanium white powder (Pt/Ce/Cu/TiO
2) catalyst composite.
The invention has the beneficial effects as follows
1) adopted the abundant the most secondary catalytic metal of rare earth metal cerium of output in domestic, promoted the stability of nitrate when the lean-combustion engine operating condition, be beneficial to the benefit and the reduction of oxynitrides, and obviously reduced the temperature of the harmless conversion of oxynitrides.
2) the present invention adopts stable metal Cu as anti-sulfur additives, has obviously improved the ability of the sulfur poisoning-resistant of catalyst own.
3) through using the method for secondary catalyst (Ce), obviously reduce the use amount of precious metals pt in the manufacture process of catalyst, reduced the catalyst cost.
4) analog result and preliminary experimental result show Pt/Ce/Cu/TiO
2Catalyst can be under lower temperature conditions (100-350 ℃), to the NO in the lean-burn gasoline motor exhaust
xCarried out efficient reduction.
Description of drawings
Accompanying drawing is catalyst composite of the present invention and existing three-way catalyst complex (Pt/Ba/Al
2O
3) NO
xHeat is overflowed contrast experiment's curve map.
The specific embodiment
1, with 15g nano grade titanium white powder (TiO
2) to immerse be that the concentration of 35 grams, 5 brochanites dissolving is 75% copper-bath, room temperature (18-25 ℃) is flooded more than 3 hours.Room temperature is rotated drying to solution.Titanium white powder carrier granular after the drying is put into drying baker (110 ℃) and is carried out 15 hours oven dry, and the particle after the oven dry carries out 7 hours roasting in Muffle furnace (800 ℃), and the acquisition load capacity is 10% Cu/TiO
2Composite oxides.
2, through the Cu/TiO after curing
2The concentration that composite oxides immerse 24 gram rare earth cerium salt dissolvings is in 55% rare earth cerium salt (cerous acetate) aqueous solution, room temperature dipping 5 hours.Pass through the Ce/Cu/TiO that can obtain load capacity 5% with embodiment 1 identical dehydration, oven dry, calcining process
2Catalyst composite.
3, with the 5Ce/10Cu/TiO for preparing
2The concentration that catalytic composite immerses 1 gram platinum nitrate salt dissolving is to keep 3 hours in 75% the platinum nitrate salting liquid, is 1% Pt/Ce/Cu/TiO through obtaining load capacity with instance 1 identical dehydration, oven dry, roasting technique
2Catalyst solid.
The effect experimental example
1. in special purpose reactor, the adsoption catalyst solid is carried out the adsorption capacity test.
With the complex that carries catalyst 150mg of the present invention, the composition of test mixing gas is: NO=500ppm, NO
2=500ppm, O
2=10%, use N
2Ratio gas as test gas.The speed of mixed airflow is 10m/s during test, Range of measuring temp 100-400 ℃.Under the different temperatures, at nitrogen oxide adsorbance (the μ molNO of 30min measurement
XG
-1), as shown in table 1.
Table 1.NO
XAbsorption scale with temperature
2. the NO of catalyst composite of the present invention and existing three-element catalytic agent carrier
xHeat is overflowed the contrast experiment
With carrying a catalyst 200mg complex of the present invention, under 100 ℃ of temperature with NO and the O of 1000ppm
2Place closed container to keep 5h, use inert gas Ar that catalyst composite is blown to room temperature.Temperature rise with 10 ℃/min is warming up to 800 ℃ with catalyst composite.Pt/Ba/Al with prior art
2O
3(carrying capacity is 1wt.Pt) is with above-mentioned identical process, NO
xThe relation of overflowing with temperature is shown in the accompanying drawing.
3. the NO of catalyst composite of the present invention and existing three-element catalytic agent carrier
xReduction reaction contrast experiment
With the Pt/Ba/Al that carries catalyst 100mg complex of the present invention and prior art
2O
3(carrying capacity is 1wt.Pt) carried out NO respectively in special purpose reactor
xReduction reaction experiment.Consisting of of reaction mixture gas: [NO]=1000ppm, [O
2]=10%.N
2As make-up gas, the speed of gaseous mixture is 10m/s, and reaction temperature is 100-400 ℃.Two kinds of different catalysts under different temperatures to NO
xClean-up effect as shown in table 2.
The catalytic effect table of table 2 different catalysts under different temperatures
Claims (2)
1. lean-burn gasoline motor exhaust denitration catalyst complex; It is characterized in that: form by cellular titanium white powder carrier with attached to the metal platinum on the carrier, rare earth metal cerium and metallic copper, the parts by weight ratio of each raw material consumption of catalyst is: metal platinum 4-8 weight portion, rare earth metal cerium 30-90 weight portion, metallic copper 80-130 weight portion.
2. the described lean-burn gasoline motor exhaust of claim 1 a denitration catalyst compound system Preparation Method comprises the steps:
(1) be that to immerse concentration be in 75% the 5 brochanite solution for the honeycomb support of base material with titanium white powder; Under 18-25 ℃ of condition, keep 3-5 hour time; Put into drying baker then and carry out 12-15 hour oven dry 85-110 ℃ of scope; Carrier after the oven dry is gone into Muffle furnace in 500-800 ℃ of scope, carry out 5-7 hour roasting, obtain copper/titanium white powder catalyst composite;
(2) will immerse in the rare earth cerium solution that concentration is 45-55% and soak 5-7 hour under 18-25 ℃ of condition through step (1) formation copper/titanium white powder catalyst composite; Here the cerium salt that is adopted is meant cerous acetate; Put into drying baker then and carry out 12-15 hour oven dry 85-110 ℃ of scope; Carrier after the oven dry is gone into Muffle furnace in 500-800 ℃ of scope, carry out 5-7 hour roasting, form cerium/copper/titanium white powder catalyst composite;
(3) it is in the platinum nitrate salting liquid of 55-75% that the cerium/copper that step (2) is obtained/titanium white powder catalyst composite immerses concentration; Soaked 3-5 hour under the 18-25 ℃ of condition; Put into drying baker then and carry out 12-15 hour oven dry 85-110 ℃ of scope; Carrier after the oven dry is gone into Muffle furnace in 500-800 ℃ of scope, carry out 5-7 hour roasting, promptly make lean-burn gasoline motor exhaust denitration platinum/cerium/copper/titanium white powder catalyst composite.
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|---|---|---|---|
| CN2011100918382A CN102728382A (en) | 2011-04-13 | 2011-04-13 | Catalytic complex for denitration of lean burn gasoline engine exhaust and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100918382A CN102728382A (en) | 2011-04-13 | 2011-04-13 | Catalytic complex for denitration of lean burn gasoline engine exhaust and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724160A (en) * | 2004-07-19 | 2006-01-25 | 中国科学院生态环境研究中心 | Catalytic decomposition NO under the excess oxygen xMetal exchange and metal load molecular sieve type catalyst |
| CN101474553A (en) * | 2009-01-17 | 2009-07-08 | 汕头大学 | Three-effect catalyst for purifying exhaust of lean-burn automotive and preparation method thereof |
| CN101618323A (en) * | 2009-07-23 | 2010-01-06 | 东南大学 | Structural catalyst for catalyzing and reducing nitrogen oxide and preparation method thereof |
| CN101722010A (en) * | 2009-09-30 | 2010-06-09 | 中国科学院生态环境研究中心 | Novel nitrogen oxide storage and reduction catalyst for exhaust gas purification of lean burn gasoline engine or diesel engine |
| CN101829579A (en) * | 2010-05-25 | 2010-09-15 | 上海应用技术学院 | Preparation method and application of cerium-zirconium composite oxide catalyst loaded with copper oxide |
-
2011
- 2011-04-13 CN CN2011100918382A patent/CN102728382A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724160A (en) * | 2004-07-19 | 2006-01-25 | 中国科学院生态环境研究中心 | Catalytic decomposition NO under the excess oxygen xMetal exchange and metal load molecular sieve type catalyst |
| CN101474553A (en) * | 2009-01-17 | 2009-07-08 | 汕头大学 | Three-effect catalyst for purifying exhaust of lean-burn automotive and preparation method thereof |
| CN101618323A (en) * | 2009-07-23 | 2010-01-06 | 东南大学 | Structural catalyst for catalyzing and reducing nitrogen oxide and preparation method thereof |
| CN101722010A (en) * | 2009-09-30 | 2010-06-09 | 中国科学院生态环境研究中心 | Novel nitrogen oxide storage and reduction catalyst for exhaust gas purification of lean burn gasoline engine or diesel engine |
| CN101829579A (en) * | 2010-05-25 | 2010-09-15 | 上海应用技术学院 | Preparation method and application of cerium-zirconium composite oxide catalyst loaded with copper oxide |
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Application publication date: 20121017 |