CN101767000A - Direct oxidation and combustion catalyst of exhaust carbon fume of diesel vehicle and preparation method thereof - Google Patents
Direct oxidation and combustion catalyst of exhaust carbon fume of diesel vehicle and preparation method thereof Download PDFInfo
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- CN101767000A CN101767000A CN201010039192A CN201010039192A CN101767000A CN 101767000 A CN101767000 A CN 101767000A CN 201010039192 A CN201010039192 A CN 201010039192A CN 201010039192 A CN201010039192 A CN 201010039192A CN 101767000 A CN101767000 A CN 101767000A
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- catalyst
- diesel vehicle
- direct oxidation
- exhaust carbon
- carbon fume
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Abstract
The invention discloses a direct oxidation and combustion catalyst of the exhaust carbon fume of a diesel vehicle and a preparation method thereof. A catalyzing material comprises an oxide carrier MO2 and a bimetal oxide active component AxByOz and has the structure of AxByOz/MO2. A and B are two kinds of metal from La, Ce, Fe, K and Cu, and MO2 is an oxide carrier, such as TiO2, gamma-Al2O3, CeO2, ZrO2, and the like. In the preparation method, ionic solutions of A and B and a complexing agent, such as citric acid, urea, PVP, oxalic acid, and the like form a complexing solution; one of the oxides is added during mechanical stirring so as to be fully adsorbed; then, the solution is filled into a muffle furnace of 500-700 DEG C and rapidly reacts to be decomposed, and an active component is synthesized in situ on the surface of the oxide. The catalyzing material can effectively reduce the oxidation and combustion temperature of carbon fume and oxygen, improve the passive regeneration efficiency of the carbon fume and achieve the aim of purifying the exhaust carbon fume of the diesel vehicle. The invention improves the dispersibility of the catalyst, overcomes the defects of small specific surface area and poor dispersion of composite oxide and has simple process, high repeatability and strong operability.
Description
Technical field
The present invention relates to a kind of catalysis material and preparation method thereof, particularly relate to a kind of catalysis material of reducing exhaust carbon fume of diesel vehicle and oxygen to directly oxidize ignition temperature and preparation method thereof that is used to.
Background technology
Along with warming of global climate, carbon emission becomes the focus that the whole world is paid close attention to.The power train in vehicle application that Diesel engine is considered to alleviate greenhouse effects and oil crisis will be subjected to application more and more widely.The content of exhaust gas from diesel vehicle CO, HC only is 1/10 of gasoline car, but soot emissions reaches tens times more than of the gasoline car discharging.In the past few decades, we often can see that diesel vehicle afterbody black smoke is billowing, on the one hand severe contamination environment, greatly limited the application of diesel car on the other hand.In recent years, along with the lifting of engine technology, the phenomenon that black smoke is billowing becomes history.But along with the lifting of environmental protection consciousness, the soot emissions that relies on emission controls by improving combustion to reach merely can't satisfy strict Abgasgesetz, and the soot post-processing technology becomes the effective means that satisfies Europe IV, Europe V Abgasgesetz.The most effective post-processing technology of control soot emissions is exactly the carbon soot particles trapping technique at present.This technology, owing to carbon soot particles can't pass through from the DPF inwall more greatly, thereby is dammed when DPF is passed through in exhaust by settling grain catcher (DPF) at the diesel engine truck exhaust pipe, and sedimentation is collected among the DPF.Make the soot generation oxidizing fire of collecting among the DPF by the regeneration means then, reach the purpose of purifying soot.Therefore, the regeneration of DPF becomes the key of this technology, and passive regeneration is the simplest in all regeneration means, need not a kind of of control strategy.It reduces the oxidizing temperature of soot by at the inner coating of DPF one deck oxidize soot catalyst, reaches the temperature of blast pipe, and oxidizing fire takes place.Do not having under the situation of catalyst, the peak temperature of directly reaction takes place at 600-700 ℃ in soot and oxygen, soot and NO
2The peak temperature that reacts is about 300 ℃.And therefore the diesel engine truck exhaust temperature, realize that the direct oxidation of soot has bigger difficulty generally 150 ℃ of-400 ℃ of scopes, and the research of the relevant oxidize soot of reporting at present nearly all concentrates on soot and NOx purifies simultaneously.
Application number is to disclose a kind of exhaust gas from diesel vehicle carbon granule burning that is used in 200410074223.9 the Chinese patent, the perovskite or the perovskite-like structure nanocatalyst that are made of rare earth metal, transition metal, alkali metal or alkaline-earth metal etc.This catalyst is contacting with the carbon granule pine, when reaction atmosphere is O2, NO coexistence, the oxidizing temperature of carbon granule can be reduced by 250 ℃, has obtained carbon granule and NOx while clean-up effect preferably.
The Huang Zhen seminar of Shanghai Communications University has also carried out the research work that a large amount of soots and NOx purify simultaneously.Seminar is mainly with the synthetic ABO of elements such as La, K, Cu, Fe, Mn
3, A
2BO
4, AB
2O
4The composite oxide catalysts of structure.Such oxide catalyst purifies simultaneously to soot and NOx has excellent catalytic activity.
In addition, the seminar that Zhao Zhen, D.Fino, M.J.Ill á n-G ó mez, S.Kureti etc. lead has all carried out a large amount of work in this field, and has obtained the excellent research result.But the research by Souzana Lorentzou etc. as can be known, and the regeneration of soot comprises the reaction of two aspects, i.e. the oxidation reaction of soot and NOx and soot and O
2Direct oxidation reaction.In the research, they will have the catalyst coated of the highest soot and NOx transformation efficiency at the DPF inwall, be not the highest total the result is coated with the regeneration efficiency of the DPF of this kind catalyst, and its reason is exactly that this kind catalyst is lower to the direct oxidation activity of soot.Therefore, soot and O
2Direct oxidation the regeneration of soot is had crucial effects equally.
Qing Liang etc. pass through at CeO
2Middle doped with Cu, Mn prepare the oxidize soot catalyst, and this catalyst can be reduced to the direct oxidation initial temperature of soot 480 ℃ when contacting with the soot pine, and maximum temperature is reduced to 500 ℃.But in actual applications, still be difficult to satisfy the application request of diesel vehicle.
Summary of the invention
The purpose of this invention is to provide a kind of soot direct oxidation catalyst that satisfies the diesel engine truck exhaust temperature range.This catalyst is under loose contact conditions, soot direct oxidation initial temperature can be reduced to 250 ℃, maximum temperature is reduced to about 450 ℃, greatly reduce the direct oxidation temperature of soot, make soot rely on the diesel engine truck exhaust temperature that direct oxidation can take place, improve the regeneration efficiency of soot, satisfy the application demand of diesel vehicle.
Catalyst provided by the present invention is that a kind of composite oxide catalysts that does not contain noble metal contains active component and oxide carrier two parts, and catalyst structure is AxByOz/MO
2, wherein y is 1 with the x ratio: 0.5-2.
Bimetal composite oxide active component among the present invention is that A, B are wherein two kinds of La, Ce, Fe, K, Cu.
Oxide M O among the present invention
2Be TiO
2, γ-Al
2O
3, CeO
2Or ZrO
2In any one.
By binding soln firing method and infusion process AxByOz composite oxides original position is synthesized at oxide surface among the present invention.Concrete preparation process is as follows:
1) according to design flow the slaine of A, B is mixed with the aqueous solution, adds a certain amount of complexing agent then and make it stable, form metal complex solution with complexing of metal ion.
2) oxide with aequum adds metal complex solution, and mechanical agitation makes oxide that fully absorption take place, and forms the reaction solution of catalyst.
3) reaction solution is inserted the Muffle furnace of 500-700 ℃ of constant temperature, solution burns rapidly at oxide surface, decomposes, stable, forms A, B composite oxides, keeps reaction 20-60min.After finishing, reaction obtains even, the loose catalyst fines of color.
The complexing agent that the present invention uses is conventional organic complexing agent, as citric acid, urea, polyvinylpyrrolidone, oxalic acid etc.The mol ratio of complexing agent and A, B metal ion total amount is 1.0-3.5 in the complex solution.Wherein preferred 1.5-3.0, reaction solution complete decomposition under this condition, response intensity is suitable, helps the formation of composite oxides.
The present invention has significantly improved the specific area of catalyst by at oxide surface carrying bimetallic composite oxides, has improved the dispersiveness of catalyst, and it is little to have overcome the composite oxides specific area, the characteristics of poor dispersion.The characteristics of binding soln firing method and solution dipping method in the preparation process, the original position synthetic catalyst, technology is simple, and repeatability is high, strong operability.The catalyst of preparation with simulation soot Printex-U pine contact conditions under, have good catalytic activity, catalyst is normally arranged under the warm condition and O at diesel vehicle
2The generation direct oxidation is reacted, and has improved the regeneration efficiency of soot, effectively realizes the passive regeneration of DPF.
Description of drawings
Fig. 1 is an activity of such catalysts evaluation result schematic diagram.
The specific embodiment
Catalyst activity is estimated:
Use ChemBET-3000 type chemisorbed instrument to carry out temperature programmed oxidation (TPO) evaluation.With the maximum temperature (Tp) of the initial reaction temperature (Ti) of TPO response curve starting point correspondence and response curve peak value correspondence as the activity of such catalysts evaluation index.
Adopt Printex-U carbon simulation diesel vehicle soot in the evaluation.Concrete operation method at first mixes with U carbon catalyst by 10: 1 weight ratio, be better simulating actual conditions, hybrid mode adopts the pine contact, in the mixed process catalyst and U carbon are put into the planetary ball mill jar that does not add bead, the setting rotating speed is 300r/min, time is 10min, realizes mixing naturally of catalyst and U carbon.Take by weighing the sample that 0.11g mixes then and put into U type quartz ampoule, feed 5%O
2The reaction atmosphere of+He, gas overall flow rate 80ml/min, 10 ℃/min of heating rate, Range of measuring temp is a room temperature to 900 ℃, adopts the TCD change in detection signal.
Case study on implementation 1
Press La, 1: 1 amount of Ce mol ratio, take by weighing lanthanum nitrate, cerous nitrate respectively, add the metal ion solution that deionized water is prepared into 2mol/L, press La then
+, Ce
3+The amount that metal ion total amount mol ratio is 1 times adds the PVP complexing agent, mechanical agitation 30min, and the back adds 100gTiO
2Powder, mechanical agitation 1h obtains reaction solution, after change reaction solution the Muffle furnace of 600 ℃ of constant temperature over to, reaction 30min.Obtain LaCeO
3/ TiO
2Catalyst.
The activity of such catalysts evaluation result is seen Fig. 1, at catalyst and soot pine contact conditions, adds LaCeO
3/ TiO
2Behind the catalyst, the initial oxidation temperature of soot (Ti) is 400 ℃, and maximum temperature (Tp) is 550 ℃.
Case study on implementation 2
Press La, 1: 1 amount of Fe mol ratio, take by weighing lanthanum nitrate, ferric nitrate respectively, add the metal ion solution that deionized water is prepared into 2mol/L, press La then
+, Fe
3+Amount that metal ion total amount mol ratio is 1.5 times adds the urea complexation agent, mechanical agitation 40min, the back adds the 100gAl2O3 powder, mechanical agitation 1.5h obtains reaction solution, after change reaction solution over to the Muffle furnace of 650 ℃ of constant temperature, reaction 20min.Obtain LaFeO3/Al
2O
3Catalyst.
The activity of such catalysts evaluation result is seen Fig. 1, at catalyst and soot pine contact conditions, adds LaFeO
3/ Al
2O
3Behind the catalyst, the initial oxidation temperature of soot (Ti) is 400 ℃, and maximum temperature (Tp) is 450 ℃.
Case study on implementation 3
Press K, 1: 2 amount of Cu mol ratio, take by weighing potassium nitrate, copper nitrate respectively, add the metal ion solution that deionized water is prepared into 2mol/L, press K then
+, Cu
2+The amount that metal ion total amount mol ratio is 2 times adds citric acid complexing agent, mechanical agitation 30min, and the back adds 100g ZrO
2Powder, mechanical agitation 1h obtains reaction solution, after change reaction solution the Muffle furnace of 550 ℃ of constant temperature over to, reaction 40min.Obtain KCu
2O
4/ ZrO
2Catalyst.
The activity of such catalysts evaluation result is seen Fig. 1, at catalyst and soot pine contact conditions, adds KCu
2O
4/ ZrO
2Behind the catalyst, the initial oxidation temperature of soot (Ti) is 210 ℃, and maximum temperature (Tp) is 490 ℃.
As can be seen from Figure 1, when not adding catalyst, the direct oxidation initial temperature of soot and oxygen is 500 ℃, and maximum temperature is 700 ℃.Catalyst disclosed by the invention can be reduced to the direct oxidation initial temperature of soot 210 ℃-400 ℃, has reduced by 290 ℃-100 ℃, and maximum temperature is reduced to 450-550 ℃, 150 ℃-250 ℃ have been reduced, have very high catalytic activity, can improve the passive regeneration of DPF, promote its application.
Claims (10)
1. exhaust carbon fume of diesel vehicle direct oxidation catalyst, it is characterized in that: be made up of active component and oxide carrier two parts, catalyst structure is AxByOz/MO
2
2. exhaust carbon fume of diesel vehicle direct oxidation catalyst according to claim 1 is characterized in that: y and x ratio are 1 in the described catalyst structure: 0.5-2.
3. exhaust carbon fume of diesel vehicle direct oxidation catalyst according to claim 1 is characterized in that: described bimetal composite oxide active component is that A, B are wherein two kinds of La, Ce, Fe, K, Cu.
4. exhaust carbon fume of diesel vehicle direct oxidation catalyst according to claim 1 is characterized in that: described oxide M O
2Be TiO
2, γ-Al
2O
3, CeO
2Or ZrO
2In any one.
5. one kind as each described exhaust carbon fume of diesel vehicle direct oxidation catalyst of claim 1 to 4, it is characterized in that: this catalyst is as the catalyst that reduces exhaust carbon fume of diesel vehicle direct oxidation ignition temperature.
6. exhaust carbon fume of diesel vehicle direct oxidation Preparation of catalysts method is characterized in that may further comprise the steps:
1) be that A, B and oxide are MO with active component
2The catalyst of carrier, its structure are AxByOz/MO
2, according to design flow the slaine of A, B is mixed with the aqueous solution, add complexing agent then and make it stable with complexing of metal ion, form metal complex solution;
2) with MO
2TiO
2, γ-Al
2O
3, CeO
2Or ZrO
2In any one add above-mentioned complex solution, evenly stir, form reaction solution;
3) above-mentioned reaction solution is inserted the Muffle furnace of 500～700 ℃ of constant temperature, the decomposition in situ generated time is 20-60min, forms A, B composite oxides, obtains even, the loose catalyst fines of color after reaction is finished.
7. a kind of exhaust carbon fume of diesel vehicle direct oxidation Preparation of catalysts method according to claim 6 is characterized in that: described active component A, B are wherein two kinds of La, Ce, Fe, K, Cu.
8. a kind of exhaust carbon fume of diesel vehicle direct oxidation Preparation of catalysts method according to claim 6, it is characterized in that: the mol ratio of described complexing agent and A, B metal ion total amount is 1.0-3.5.
9. a kind of exhaust carbon fume of diesel vehicle direct oxidation Preparation of catalysts method according to claim 6 is characterized in that: described MO
2Be TiO
2, γ-Al
2O
3, CeO
2Or ZrO
2In any one.
10. a kind of exhaust carbon fume of diesel vehicle direct oxidation Preparation of catalysts method according to claim 6, it is characterized in that: described complexing agent is citric acid, urea, polyvinylpyrrolidone or oxalic acid.
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|---|---|---|---|
| CN201010039192A CN101767000A (en) | 2010-01-20 | 2010-01-20 | Direct oxidation and combustion catalyst of exhaust carbon fume of diesel vehicle and preparation method thereof |
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|---|---|---|---|
| CN201010039192A CN101767000A (en) | 2010-01-20 | 2010-01-20 | Direct oxidation and combustion catalyst of exhaust carbon fume of diesel vehicle and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104759281A (en) * | 2015-03-11 | 2015-07-08 | 江苏大学 | Preparation method of composite oxide catalyst used for purifying diesel engine |
| CN104998626A (en) * | 2015-07-29 | 2015-10-28 | 江苏大学 | Heterogeneous catalyst for diesel engine NOx emission aftertreatment and preparation method thereof |
| CN105565806A (en) * | 2014-12-08 | 2016-05-11 | 比亚迪股份有限公司 | Ceramic and preparation method thereof |
| CN108147455A (en) * | 2017-12-13 | 2018-06-12 | 昆明贵研催化剂有限责任公司 | A kind of preparation method of the mesoporous aluminium base RE composite of high thermal stability |
-
2010
- 2010-01-20 CN CN201010039192A patent/CN101767000A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105565806A (en) * | 2014-12-08 | 2016-05-11 | 比亚迪股份有限公司 | Ceramic and preparation method thereof |
| CN104759281A (en) * | 2015-03-11 | 2015-07-08 | 江苏大学 | Preparation method of composite oxide catalyst used for purifying diesel engine |
| CN104998626A (en) * | 2015-07-29 | 2015-10-28 | 江苏大学 | Heterogeneous catalyst for diesel engine NOx emission aftertreatment and preparation method thereof |
| CN108147455A (en) * | 2017-12-13 | 2018-06-12 | 昆明贵研催化剂有限责任公司 | A kind of preparation method of the mesoporous aluminium base RE composite of high thermal stability |
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Application publication date: 20100707 |