CN103977792A - Composite oxide catalyst for catalytic combustion of soot in diesel engine exhaust, and preparation method of catalyst - Google Patents
Composite oxide catalyst for catalytic combustion of soot in diesel engine exhaust, and preparation method of catalyst Download PDFInfo
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- CN103977792A CN103977792A CN201410221236.8A CN201410221236A CN103977792A CN 103977792 A CN103977792 A CN 103977792A CN 201410221236 A CN201410221236 A CN 201410221236A CN 103977792 A CN103977792 A CN 103977792A
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Abstract
The invention relates to a composite oxide catalyst for catalytic combustion of soot particles in diesel engine exhaust. The composite oxide catalyst has the following composition: Ce2O2-MOx/ Lax' A(1-x)' Mny B(1-y) O3, wherein M is one or more in Zr, Pr, Sm or Y, A is one or more in K, Ca, Ba or Sr, and B is one or more in Cr, Fe, Co or Ni. The soot combustion catalyst has good performance of removing soot in a catalytic way, and is low in cost, simple in preparation process and easy in industrial application.
Description
Technical field
The present invention relates to a kind of composite oxide catalysts for diesel engine vent gas soot catalytic combustion, be mainly used in the low-temperature catalyzed elimination of carbon soot particles in diesel engine vent gas.
Background technology
The carbon soot particles of exhaust emissions of diesel engine has less particle diameter, not only can enter human lung with breathing, causes respiratory disease, also can be suspended in atmosphere simultaneously, and be one of major pollutants that cause haze.Adopt particulate matter trap (DPF) to control at present the highest vent gas treatment product of diesel vehicle PM discharge efficiency, can reach more than 90% the arresting efficiency of PM.Because the exhaust temperature of diesel engine vent gas will be lower than the burning/oxidizing temperature of carbon soot particles, directly oxidized or generation burning of the carbon soot particles therefore accumulating in DPF.When PM in DPF accumulates to when a certain amount of, can make exhaust back pressure too high, now just need to change DPF or the processing of regenerating.The renovation process of DPF is divided into initiative regeneration and the large class of passive regeneration two: initiative regeneration is to utilize external energy (as: change of electric heater, burner or engine operating condition to improve delivery temperature) to make the temperature of DPF inside reach the ignition temperature of soot and the regeneration carried out; Passive regeneration refers to that the energy that utilizes diesel engine truck exhaust itself to have regenerates.Adopt catalyst, can reduce significantly the ignition temperature of soot, be expected to make its just can be oxidized/combustion reaction in the temperature range of diesel exhaust gas, thereby reach the object of cyclic regeneration.
The selected catalyst of soot catalytic combustion can be divided into noble metal catalyst, base metal catalysts and catalyst of transition metal oxide.Wherein noble metal catalyst (as Pt) be at present the highest active catalyst [
appl. Catal.B, 1998,18,183-188], but Precious Metals Resources is limited, and cost is higher.For single metal oxide, the activity of catalyst and stability are difficult to again meet the demand of practical application, therefore often improve the performance of catalyst by forming composite oxides.As at CeO
2the formation such as middle introducing Cu, Mn complex rare-earth oxidate containing valuable metal [
catal. Commun.9 (2008) 2428], perofskite type oxide and substituent thereof [
appl. Catal. B83 (2008) 85;
catal. Commun.,2007,8,157-161] etc.Because diesel exhaust gas temperature is generally 100 ~ 450
oC, run at high speed and can reach 600
oChigh temperature, so require catalyst not only to there is low temperature active, to reduce the ignition temperature of soot, also to there is high-temperature stability, to meet the long-term requirement using of diesel engine simultaneously.
Meanwhile, Gu soot catalytic combustion is typically gas-solid-reaction simultaneously, the exposure level between catalyst and soot, particularly, under loose contact conditions, the contact performance between soot and catalyst has significant impact to the activity of carbon-smoke combustion.By introducing low-melting alkali metal oxide (as Li, K etc.), utilize its good mobile performance having, can significantly improve the contact performance between catalyst and carbon soot particles, improve the carbon-smoke combustion performance of catalyst.
Therefore develop and there is good low temperature active and the soot combustion catalyst of high stability simultaneously, become the difficult point of research.
Summary of the invention
The object of the present invention is to provide a kind of composite oxide catalysts that can be used for diesel engine vent gas carbon soot particles catalytic combustion, can reduce the ignition temperature of diesel vehicle soot particle, compared with the prior art, the substantive distinguishing features that the present invention has is:
(1) this catalyst has high carbon-smoke combustion activity, and under loose contact conditions, activity and the loaded Pt catalyst of carbon-smoke combustion are suitable, T
50can be reduced to 410
oc;
(2) catalyst has good high-temperature stability, and the poisoning ability of anti-S;
(3) without using noble metal, reduced preparation cost, preparation process letter, single easy operating, reproducible.
The present invention realizes above-mentioned purpose by changing catalysis composition and preparation method.
Catalyst of the present invention mainly contains two parts composition: CeO
2base composite oxidate and perovskite composite oxide, the complex method of the two can significantly impact activity and the stability of catalyst simultaneously, and the composition of catalyst also has influence on the best complex mode of catalyst.
The composition of catalyst of the present invention can be expressed as: CeO
2-MO
x/ La
x'a
1-x'mn
yb
1-yo
3+ δ: wherein M is one or more in Zr, Pr, Sm or Y; A is one or more in K, Ca, Ba, Sr; B is one or more in Cr, Fe, Co or Ni.
Wherein CeO
2-MO
xthe shared percentage by weight of composite oxides is 5%-60%, and MOx is at CeO
2the shared mol ratio of base composite oxidate is 0%-50%; La
x'a
1-x'mn
yb
1-yo
3+ δcomposite oxides are 40%-95% at the shared percentage by weight of catalyst, at La
x'a
1-x'mn
yb
1-yo
3+ δin: the shared mol ratio of A is 0%-20%, and B proportion is 0%-80%.
Technology path prepared by catalyst of the present invention is:
The preparation of perovskite composite oxide: take in proportion corresponding soluble salt and citric acid, be dissolved in the mixed liquor of deionized water and organic solvent, stirring in water bath is to forming gel; 120
oc is dry is placed on roasting in air, 500 ~ 800
oc roasting 1-5 hour.
Carrier surface is modified: by a certain amount of surfactant dissolves, add La
xa
1-xmn
yb
1-yo
3, through stirring, filter, washing and dry after obtain the La of finishing
xa
1-xmn
yb
1-yo
3.Surfactant adopts one or more in PVP, PEG or Tween-80.
CeO
2-MO
x/ La
xa
1-xmn
yb
1-yo
3the preparation of catalyst: adopt infusion process preparation, taking the nitrate solution of M and Ce as precursor, adding organic solvent is diffusant, adds while stirring the made La of getting ready
xa
1-xmn
yb
1-yo
3, stir after 2 ~ 5 hours, leave standstill 12 h, then dry, 400
oc ~ 600
oc roasting.Or, adopt deposition-precipitation method preparation, taking the nitrate solution of M and Ce as precursor, adding organic solvent is diffusant, adds while stirring the made La of getting ready
xa
1-xmn
yb
1-yo
3, then under stirring condition, adding precipitating reagent, precipitation completely rear continuation stirs 2 ~ 5 hours, and all the other steps are the same.
Detailed description of the invention
In order to be illustrated more clearly in the present invention, enumerate following examples, but it is without any restrictions to scope of the present invention.
Embodiment 1
Take a certain amount of lanthanum nitrate, manganese nitrate and chloroplatinic acid according to stoichiometry mol ratio, the content of chloroplatinic acid is 0.5% according to Pt content in final catalyst, be dissolved in and in deionized water, be made into 0.5mol/L solution, the citric acid of 1.2 times of metal ion moles is joined to stirring and dissolving in solution, add a certain amount of dispersant, in stirred in water bath to colloidal sol; Gained colloidal sol is placed in 120
oCunder be dried, finally in air, roasting forms 0.5%Pt-LaMnO
3, sintering temperature is 650
oc.
Evaluating catalyst method: soot catalytic oxidation carries out performance evaluation in atmospheric fixed bed stainless steel reaction pipe, contact conditions is loose contact, catalyst and soot mass ratio are 9:1.O in unstripped gas
2content is that 8%, NO is 500ppm, and all the other are Ar, and gas flow rate is 100mL × min
-1.Use GC-9790 type gas chromatograph, Porapak Q packed column, hydrogen flame detector (FID), methane conversion furnace temperature is 360
oc, detects CO and CO online
2.T
50temperature when corresponding soot conversion ratio is 50%.
Active testing shows, uses this method to prepare gained 0.5%Pt-LaMnO
3the T of catalyst
50be 415
oc.
Embodiment 2
Adopt above-mentioned sol-gal process to prepare LaMnO
3composite oxide catalysts, catalyst activity evaluation method is with embodiment 1, gained LaMnO
3the T of composite oxide catalysts
50be 436
oc.
Embodiment 3
Adopt above-mentioned sol-gal process to prepare LaMnO
3composite oxides, after pretreatment, adopt infusion process to prepare CeO
2/ LaMnO
3, wherein CeO
2weight be LaMnO
320%.Precursor salt using ammonium ceric nitrate as Ce, adding organic solvent is diffusant, adds while stirring the made LaMnO getting ready
3, stir after 2 ~ 5 hours, leave standstill 12 h, then dry, 500
oc roasting.
Catalyst activity evaluation method is with embodiment 1, gained CeO
2/ LaMnO
3the T of catalyst
50be 410
oc.
Embodiment 4
Adopt above-mentioned sol-gal process to prepare LaMnO
3composite oxides, after pretreatment, adopt infusion process to prepare CeO
2/ LaMnO
3, wherein CeO
2weight be LaMnO
340%.Precursor salt using ammonium ceric nitrate as Ce, adding organic solvent is diffusant, adds while stirring the made LaMnO getting ready
3, stir after 2 ~ 5 hours, leave standstill 12 h, then dry, 500
oc roasting.
Catalyst activity evaluation method is with embodiment 1, gained CeO
2/ LaMnO
3the T of catalyst
50be 412
oc.
Embodiment 5
By the H in embodiment 1
2ptCl
66H
2o changes KNO into
3, take according to certain mol ratio, finally obtain the La of A position doping
0.9k
0.1mnO
3composite oxides.
Catalyst activity evaluation method is with embodiment 1, gained La
0.9k
0.1mnO
3the T of catalyst
50be 420
oc.
Embodiment 6
By the KNO in embodiment 3
3change Fe (NO into
3)
3, take according to certain mol ratio, finally obtain the LaMn of B position doping
0.5fe
0.5o
3composite oxides.
Catalyst activity evaluation method is with embodiment 1, gained LaMn
0.5fe
0.5o
3the T of catalyst
50be 425
oc.
Claims (7)
1. for a composite oxide catalysts for carbon-smoke combustion, can be used for the catalytic combustion of diesel engine vent gas carbon soot particles, there is high activity and stability, it is characterized in that:
Consisting of of catalyst: CeO
2-MO
x/ La
xa
1-xmn
yb
1-yo
3,
M is one or more in Zr, Pr, Sm or Y,
A is one or more in K, Ca, Ba, Sr,
B is one or more in Cr, Fe, Co or Ni.
2. according to a kind of composite oxide catalysts for carbon-smoke combustion described in right 1, it is characterized in that CeO
2-MO
xin catalyst, shared weight ratio is 5%-60%, MO
xat CeO
2-MO
xmiddle proportion is 0%-50%.
3. according to a kind of composite oxide catalysts for carbon-smoke combustion described in right 1, its feature is at La
x'a
1-x'mn
yb
1-yo
3+ δin catalyst, shared weight ratio is 40%-95%; At La
x'a
1-x'mn
yb
1-yo
3+ δin: the shared mol ratio of A is 0-20%, and B proportion is 0-80%.
4. La according to claim 3
x'a
1-x'mn
yb
1-yo
3+ δ, it is characterized in that adopting sol-gel process preparation or coprecipitation preparation, concrete preparation process comprises the following steps:
Take in proportion corresponding solvable nitrate and citric acid, be dissolved in deionized water, adding organic solvent is diffusant, and stirring in water bath is to forming gel; After dry, be placed in air 600 ~ 900
oc roasting 1-5 hour;
Or: take in proportion corresponding solvable nitrate, be dissolved in deionized water, adding organic solvent is diffusant, under agitation adds precipitating reagent, precipitation completely after, after filtration, washing, dry, be placed in air 600 ~ 900
oc roasting 1-5 hour.
5. according to a kind of composite oxide catalysts for carbon-smoke combustion described in right 1, it is characterized in that with La
x'a
1-x'mn
yb
1-yo
3+ δfor carrier, adopt maceration extract method or deposition-precipitation method to prepare CeO
2-MO
x/ La
xa
1-xmn
yb
1-yo
3, detailed process comprises:
Adopting the nitrate of M and Ce is precursor, is dissolved in deionized water, and then adding organic solvent is dispersant, under stirring condition, adds La
x'a
1-x'mn
yb
1-yo
3+ δ, stir after 2 ~ 5 hours, leave standstill 12 h, then dry, 400
oc ~ 600
oc roasting;
Or, adopt deposition-precipitation method preparation, taking the nitrate solution of M and Ce as precursor, be dissolved in deionized water, adding organic solvent is diffusant, adds while stirring La
xa
1-xmn
yb
1-yo
3, then under stirring condition, add precipitating reagent, after precipitation is complete, continue to stir after 2 ~ 5 hours, leave standstill 12 h, then filter, wash, be dried, 400
oc ~ 600
oc roasting.
6. according to the preparation method of a kind of composite oxide catalysts for carbon-smoke combustion described in right 4, it is characterized in that adopting organic solvent as diffusant, organic solvent adopts one or more in ethanol, acetone, propyl alcohol, isopropyl alcohol.
7. according to the preparation method of a kind of composite oxide catalysts for carbon-smoke combustion described in right 5, it is characterized in that adopting organic solvent as diffusant, organic solvent adopts one or more in ethanol, acetone, propyl alcohol, isopropyl alcohol, and precipitating reagent is one or more in ammonium carbonate, sodium carbonate, NaOH or ammoniacal liquor.
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| CN109012647A (en) * | 2018-07-03 | 2018-12-18 | 厦门大学 | A kind of diesel engine vent gas soot removing metal composite oxide catalyst and preparation method thereof |
| CN110075829A (en) * | 2019-06-11 | 2019-08-02 | 合肥神舟催化净化器股份有限公司 | A kind of low-temperature catalytic oxidation diesel oxidation catalyst preparation method |
| CN110102307A (en) * | 2019-04-29 | 2019-08-09 | 长安大学 | A kind of preparation method and catalyst of the catalyst for catalyzed carbon particles burning |
| CN111841572A (en) * | 2020-08-06 | 2020-10-30 | 合肥神舟催化净化器股份有限公司 | High-acidity single-coating perovskite-based ammonia oxidation catalyst for diesel engine and preparation and application methods thereof |
| WO2023065400A1 (en) * | 2021-10-22 | 2023-04-27 | 武汉工程大学 | Porous multi-doped perovskite catalyst and preparation method therefor |
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Cited By (6)
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| CN111841572A (en) * | 2020-08-06 | 2020-10-30 | 合肥神舟催化净化器股份有限公司 | High-acidity single-coating perovskite-based ammonia oxidation catalyst for diesel engine and preparation and application methods thereof |
| WO2023065400A1 (en) * | 2021-10-22 | 2023-04-27 | 武汉工程大学 | Porous multi-doped perovskite catalyst and preparation method therefor |
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