CN105214649A - Diesel vehicle exhaust carbon-smoke particulate catalytic burner - Google Patents
Diesel vehicle exhaust carbon-smoke particulate catalytic burner Download PDFInfo
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- CN105214649A CN105214649A CN201510534286.6A CN201510534286A CN105214649A CN 105214649 A CN105214649 A CN 105214649A CN 201510534286 A CN201510534286 A CN 201510534286A CN 105214649 A CN105214649 A CN 105214649A
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- catalyst
- diesel vehicle
- vehicle exhaust
- catalytic burner
- carbon
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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 open one of the present invention can process carbon soot particles simultaneously, nitrogen oxide, carbon monoxide and hydrocarbon, and there is the base metal type exhaust gas from diesel vehicle arrangement for catalytic purification of ideal effect, comprise the catalyst of cellular ceramic substrate and load, catalyst is cerium, dysprosium, the composite oxides of manganese and calcium, its molar ratio is Ce: Dy: Mn: Ca=1: 0.1-0.5: 0.2-0.8: 0.1-0.5, sol-gal process is adopted to prepare Ce-Dy-Mn-Ca? composite oxide catalysts, can be formed? Ce-Dy-Mn-Ca solid solution structure, promote Ce, Dy, Mn, collaborative and facilitation mutually is effectively played between Ca, better raising catalyst combination property.
Description
Technical field
The present invention relates to motor vehicle fittings, specifically for the catalyst of carbon soot particles in catalytic purification diesel oil vehicle exhaust.
Background technology
Carbon soot particles, nitrogen oxide, carbon monoxide and hydrocarbon in bavin, vehicles equipped with gasoline engine tail gas have become the major pollutants of urban air, these pollutants not only serious environment pollution, and are directly detrimental to health.Current China cannot provide the ripe application product simultaneously can administering this four pollutant substantially.And be applied to the three-way catalyst (namely simultaneously can administer the catalyst of nitrogen oxide, carbon monoxide and hydrocarbon) of tail-gas from gasoline automobiles purified treatment, and noble metal must be adopted as active constituent, expensive.Exhaust gas from diesel vehicle composition and gasoline car have marked difference, and three-way catalyst is not used on diesel vehicle.
Diesel vehicle realizes state IV discharge, solves mainly through EGR and SCR two schemes.EGR scheme reduces NOx by EGR, by DPF trap particulate matter and by regeneration techniques except degranulation, or adopt POC or DOC technology, operation principle and DPF similar, just particle transformation efficiency is more lower slightly, therefore generally adopts the technical scheme that DPF and EGR combines, the technical scheme also adopting EGR+DOC+PDF had, the particle conversion ratio of DPF can reach 80% ~ 90%, and when being used alone DOC or POC, particle conversion ratio is about 50%; SCR scheme is optimized by engine combustion, makes granular material dischargedly to reach laws and regulations requirement, but add the discharge of NOx, needs in gas extraction system, to install SCR system to reduce the discharge of NOx, conversion rate of NOx can be made to reach more than 85%.But two schemes price is all very expensive, domestic diesel automobile in use does not use these systems substantially, and the pollution of diesel automobile in use is very serious, and therefore the pollution problem of Low-cost solution diesel automobile in use seems very urgent.
According to prior art, hydrocarbon contained in purified treatment waste gas, carbon monoxide, nitrogen oxide, soot particle all need to use multiple catalysts, such as reduction catalyst process nitrogen oxide, oxidation catalyst processing hydrocarbons and carbon monoxide, adopt DPF or CDPF process soot particle.As the methods and apparatus disclosed such as CN104321506A, CN103582523A, CN104040125A, CN102168596A, CN101845978A, CN102597447A.
CN103498717A discloses a kind of bus DOC+CDPF diesel engine exhaust purification filtering system, be made up of the barrel-shaped inlet chamber connected successively, barrel-shaped oxidation catalyzer (DOC), barrel-shaped diesel motor black smoke catalyst filter (CDPF) and barrel-shaped discharge chamber, the carbon monoxide CO in tail gas, hydrocarbon HC, black smoke particle PM can be processed, but can not nitrogen oxide be processed.
CN102626632A discloses a kind of perovskite type catalyst La simultaneously eliminating nitrogen oxide and carbon soot particles in exhaust gas from diesel vehicle
0.9m
0.1niO
3(M=La, Li, Na, K or Rb), have activity, but nitrogen oxides treatment rate is too low nitrogen oxide and the carbon soot particles of simulation exhaust gas from diesel vehicle discharge while in eliminative reaction.
CN102188971A discloses a kind of diesel truck vent gas four-effect catalyst, this catalyst is made up of carrier magnalium hydrotalcite composite oxides and load K thereon and noble metal, four kinds of major pollutants in exhaust gas from diesel vehicle can be removed simultaneously---soot particulate (PM), nitrogen oxide (NOx), carbon monoxide (CO) and unburned hydrocarbons (HC), but the noble metal used is expensive.
CN101239313A discloses a kind of copper cerium aluminium catalyst and the preparation method that remove carbon soot particles and nitrogen oxide simultaneously.Be characterized in adopting cheap base metal salt to be raw material, Catalyst Production cost is low; Adopt the comparatively simple catalyst preparation process such as sol-gel process, coprecipitation, course of reaction easily controls, and easily realizes suitability for industrialized production.Adjust different Cu, Ce, Al mass percents, obtained CuO-CeO
2-Al
2o
3catalyst, to simulate exhaust gas from diesel vehicle for reaction atmosphere, can be reduced to close to 400 DEG C by about 550 DEG C by the ignition temperature of soot, simultaneously can reductive NO to a certain extent, but the conversion ratio of the ignition temperature of soot and NO is all unsatisfactory.
Summary of the invention
The object of the present invention is to provide one can process carbon soot particles, nitrogen oxide, carbon monoxide and hydrocarbon simultaneously, and there is the base metal type exhaust gas from diesel vehicle arrangement for catalytic purification of ideal effect.
Diesel vehicle exhaust carbon-smoke particulate catalytic burner of the present invention comprises the catalyst of cellular ceramic substrate and load, described catalyst is the composite oxides of cerium, dysprosium, manganese and calcium, its molar ratio is Ce: Dy: Mn: Ca=1: 0.1-0.5: 0.2-0.8: 0.1-0.5, and this catalyst is obtained by following methods:
In the corresponding nitrate taking cerium, dysprosium, manganese and calcium of described ratio, add and generate the citric acid that cerium citrate, citric acid dysprosium, manganese citrate and the calcium citrate First Astronautic Research Institute for Measurement and Test need 1-1.2 times of citric acid, the polyethylene glycol of citric acid weight 2-10%, soluble in waterly be made into mixed solution, stirring, evaporate to dryness, obtain gel, gel is dried 10-36 hours in 100-150 DEG C, in 300-450 DEG C of pre-burnings 0.5-2 hours, again in 550-700 DEG C of roastings 1-3 hours, after cooling, obtain Ce-Dy-Mn-Ca composite oxide catalysts;
Described catalyst is added water and is ground to average grain diameter 50-150nm, be made into the emulsion of solid content 5-20wt%, cellular ceramic substrate is immersed in emulsion dry after 2-4 days, obtains oily tail gas carbon soot particles catalytic burner.
In the present invention, cerium, dysprosium, manganese and calcium are preferably Ce: Dy: Mn: Ca=1: 0.1-0.3: 0.5-0.7: 0.1-0.3, are more preferably Ce: Dy: Mn: Ca=1: 0.15-0.25: 0.5-0.7: 0.15-0.25.
Described cellular ceramic substrate is mixed by clay and the active carbon powder ratio by weight 1 ︰ 0.5-1.5, adds water and grinds to form mud, makes after green honeycomb body through 1000-1100 DEG C of sinter moldings.
Described clay be selected from kaolin, bentonite, ball clay, atlapulgite, fire clay, viscosity marine soil, viscosity organoclay, viscosity bog soil one or more.Preferably clay is selected from kaolin or viscosity marine soil.
Described sintering process is insulation 0.5-2 hours after being warming up to 500-550 DEG C by the speed of 50-80 DEG C/h, then with the programming rate to 1000 of 80-120 DEG C/h-1100 DEG C, annealing cooling.
The consumption of rare earth metal cerium of the present invention is more, plays rare earth metal cerium (Ce) oxide and easily realizes Ce
4+with Ce
3+the feature of mutual conversion, impels manganese (Mn) oxide to strengthen the changeable speed of valence state, accelerates the redox cycle of metal oxide, thus improve the catalytic oxidation activity for soot, in addition, and Ce
2o
3also likely react with diesel oil medium sulphide content and generate stable Ce
2(SO
4)
3, this will improve the resisting sulfide poisoning capability of catalyst.
Add rare earth metal dysprosium (Dy), utilize it to have the design feature of the 4f track of 4f electronics and underfill electronics, by the lone pair electrons coordination of oxygen on this electronics and track and S=O, thus to Ce
2(SO
4)
3in SO
4 2-play stabilization, assist rare earth metal cerium to improve the resisting sulfide poisoning performance of catalyst further, stop sulfide to be oxidized into SO
2or SO
3.In addition, add the coke content that dysprosium can reduce catalyst surface, reduce the probability that catalyst active center is covered by hydrocarbon, thus the life-span of extending catalyst.
Utilize the feature that calcium (Ca) oxide ester mp is higher, effectively improve the heat endurance of catalyst.
Adopt sol-gal process to prepare Ce-Dy-Mn-Ca composite oxide catalysts, Ce-Dy-Mn-Ca solid solution structure can be formed, promote effective performance collaborative and facilitation mutually between Ce, Dy, Mn, Ca, better raising catalyst combination property.
The present invention has excellent clean-up effect to carbon soot particles, nitrogen oxide, carbon monoxide and hydrocarbon, take fire when carbon soot particles is more than 275 DEG C, can burn completely at 300-400 DEG C, hydrocarbon rises at 225 DEG C and takes fire, more than 250 DEG C conversion ratios reach 99%, CO and take fire at 250 DEG C, and more than 300 DEG C conversion ratios reach 99%, NO rises at 225 DEG C and takes fire, and between 275-400 DEG C, conversion ratio reaches about 60%.
Detailed description of the invention
Embodiment 1
The preparation of carrier: kaolin and the active carbon ratio by weight 1 ︰ 1 mixed, the grinding that adds water forms porcelain mud, and make thickness 5mm, the circular green honeycomb body of diameter 8.5cm, honeycomb hole aperture has 1mm, 1.6mm, 2.3mm, 3mm tetra-kinds of specifications respectively.1mm aperture base substrate has 236 holes, and 1.6mm aperture base substrate has 212 holes, and 2.2mm aperture base substrate has 188 holes, and 3mm aperture base substrate has 164 holes.After base substrate dries, put into kiln, after being warming up to 500 DEG C by the speed of 60 DEG C/h, be incubated 1 hour, then with the programming rate to 1050 DEG C of 100 DEG C/h, annealing cooling obtains carrier.
The preparation of catalyst: get cerous nitrate (Ce (NO
3)
36H
2o) 434 grams, dysprosium nitrate (Dy (NO)
36H
2o) 90 grams, Mn nitrate (Mn (NO
3)
24H
2o) 160 grams, calcium nitrate (Ca (NO
3)
2) 30 grams, citric acid (C
6h
8o
7) 350 grams, polyethylene glycol 20 grams, is soluble in waterly made into mixed solution, stirring, evaporate to dryness, obtain gel, dried 24 hours by gel in 110 DEG C, in 400 DEG C of pre-burnings 1 hour, then in 600 DEG C of roastings 2 hours, after cooling, obtain Ce-Dy-Mn-Ca composite oxide catalysts.
The appendix of catalyst: the water adding 10wt% in the catalyst, grinding becomes the emulsion of average grain diameter about 100 nano particle, then adds the water dilution of 8 times of emulsion weight, cellular ceramic substrate to be immersed in the emulsion of dilution 3 days, take out carrier, dry, obtain exhaust gas from diesel vehicle arrangement for catalytic purification.
The assembling of purifier: the carrier of CatalystT is fixed in cylindrical shape outer steel shell by the sequential arrangement of 1mm aperture * 2,1.6mm aperture * 1,2.3mm aperture * 1,3mm aperture * 1, leave the gap of 7-8mm between every sheet, be purified device.
Embodiment 2
The preparation of carrier: identical with embodiment 1.
The preparation of catalyst: cerous nitrate (Ce (NO
3)
36H
2o) 434 grams, dysprosium nitrate (Dy (NO)
36H
2o) 100 grams, Mn nitrate (Mn (NO
3)
24H
2o) 140 grams, calcium nitrate (Ca (NO
3)
2) 30 grams, citric acid (C
6h
8o
7) 380 grams, polyethylene glycol 30 grams, is soluble in waterly made into mixed solution, stirring, evaporate to dryness, obtain gel, dried 24 hours by gel in 110 DEG C, in 400 DEG C of pre-burnings 1 hour, then in 600 DEG C of roastings 2 hours, after cooling, obtain Ce-Dy-Mn-Ca composite oxide catalysts.
The appendix of catalyst: the water adding 10wt% in the catalyst, grinding becomes the emulsion of average grain diameter about 100 nano particle, then adds the water dilution of 12 times of emulsion weight, cellular ceramic substrate to be immersed in the emulsion of dilution 3 days, take out carrier, dry, obtain exhaust gas from diesel vehicle arrangement for catalytic purification.
The assembling of purifier: identical with embodiment 1.
Assessment of cleaning efficiency
1. combustion temperature of soot
Adopt Yuchai YC4BJ100-31 engine, 0 ﹟ diesel oil, and in diesel oil, add a small amount of lubricant to increase soot emissions, the tail gas that engine is discharged is passed into respectively the clarifier of embodiment 1 and embodiment 2, absorb temperature 100-150 DEG C, soak time 24 hours.
Adopt N
2about 10% oxygen, about 5% steam, the NO of about 100ppm and the NO of about 100ppm is added in air-flow
2become exhaust gas flow.Exhaust gas flow is heated, from 200 DEG C, is elevated to 600 DEG C by the speed of 10 DEG C/min, by after the purifier that absorbs carbon soot particles, CO in test airflow
2concentration.Test result sees the following form:
CO in air-flow
2peak concentration appear at 350 DEG C, CO subsequently
2concentration reduce gradually, do not have appearance second peak value at 550-600 DEG C, illustrate and to have burnt clean between carbon soot particles 300-400 DEG C, 275-300 DEG C time, carbon soot particles has the sign that significantly burns.
2. the purified treatment ability of couple HC, CO, NO
Burner is accessed Yuchai YC4BJ100-31 waste pipe, adopt the 0 ﹟ diesel oil adding a small amount of lubricant as fuel, engine maintains the tail gas of the rotating speed discharge of 3000 revs/min, burner front end exhaust temperature about 330 DEG C, the absorptivity of test tail gas, the content of CO, NO.
Test result sees the following form:
Test result is seen, the purification efficiency of carbon soot particles reaches 98%, and the conversion ratio that the conversion ratio that the conversion ratio of hydrocarbon reaches 95%, CO reaches about 60%, NO reaches about 70%.
Claims (7)
1. a diesel vehicle exhaust carbon-smoke particulate catalytic burner, comprise the catalyst of cellular ceramic substrate and load, it is characterized in that, described catalyst is the composite oxides of cerium, dysprosium, manganese and calcium, its molar ratio is Ce: Dy: Mn: Ca=1: 0.1-0.5: 0.2-0.8: 0.1-0.5, and this catalyst is obtained by following methods:
In the corresponding nitrate taking cerium, dysprosium, manganese and calcium of described ratio, add and generate the citric acid that cerium citrate, citric acid dysprosium, manganese citrate and the calcium citrate First Astronautic Research Institute for Measurement and Test need 1-1.2 times of citric acid, the polyethylene glycol of citric acid weight 2-10%, soluble in waterly be made into mixed solution, stirring, evaporate to dryness, obtain gel, gel is dried 10-36 hours in 100-150 DEG C, in 300-450 DEG C of pre-burnings 0.5-2 hours, again in 550-700 DEG C of roastings 1-3 hours, after cooling, obtain Ce-Dy-Mn-Ca composite oxide catalysts;
Described catalyst is added water and is ground to average grain diameter 50-150nm, be made into the emulsion of solid content 5-20wt%, cellular ceramic substrate is immersed in emulsion dry after 2-4 days, obtains oily tail gas carbon soot particles catalytic burner.
2. diesel vehicle exhaust carbon-smoke particle burning catalyst according to claim 1, is characterized in that, Ce: Dy: Mn: Ca=1: 0.1-0.3: 0.5-0.7: 0.1-0.3.
3. diesel vehicle exhaust carbon-smoke particulate catalytic burner according to claim 1, is characterized in that, Ce: Dy: Mn: Ca=1: 0.15-0.25: 0.5-0.7: 0.15-0.25.
4. arbitrary diesel vehicle exhaust carbon-smoke particulate catalytic burner according to claim 1-3, described cellular ceramic substrate is mixed by clay and the active carbon powder ratio by weight 1 ︰ 0.5-1.5, add water and grind to form mud, make after green honeycomb body through 1000-1100 DEG C of sinter moldings.
5. diesel vehicle exhaust carbon-smoke particulate catalytic burner according to claim 4; it is characterized in that, described clay be selected from kaolin, bentonite, ball clay, atlapulgite, fire clay, viscosity marine soil, viscosity organoclay, viscosity bog soil one or more.
6. diesel vehicle exhaust carbon-smoke particulate catalytic burner according to claim 5, it is characterized in that, described clay is selected from kaolin or viscosity marine soil.
7. diesel vehicle exhaust carbon-smoke particulate catalytic burner according to claim 4, it is characterized in that, described sintering process is insulation 0.5-2 hours after being warming up to 500-550 DEG C by the speed of 50-80 DEG C/h, again with the programming rate to 1000 of 80-120 DEG C/h-1100 DEG C, annealing cooling.
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|---|---|---|---|
| CN201510534286.6A CN105214649A (en) | 2015-08-27 | 2015-08-27 | Diesel vehicle exhaust carbon-smoke particulate catalytic burner |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510534286.6A CN105214649A (en) | 2015-08-27 | 2015-08-27 | Diesel vehicle exhaust carbon-smoke particulate catalytic burner |
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| CN105214649A true CN105214649A (en) | 2016-01-06 |
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| CN201510534286.6A Pending CN105214649A (en) | 2015-08-27 | 2015-08-27 | Diesel vehicle exhaust carbon-smoke particulate catalytic burner |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114029068A (en) * | 2021-12-03 | 2022-02-11 | 华设设计集团环境科技有限公司 | Catalyst for cooperative control of nitrogen oxides and particulate matters in diesel engine tail gas and preparation method and application thereof |
| CN114247448A (en) * | 2020-09-24 | 2022-03-29 | 广东加南环保生物科技有限公司 | Oxidation type catalyst for diesel engine exhaust aftertreatment and manufacturing method thereof |
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| JPH04267945A (en) * | 1991-02-22 | 1992-09-24 | Kazuyoshi Sugi | Catalyst furnace material for removing harmful component of exhaust gas |
| CN1141213A (en) * | 1995-07-21 | 1997-01-29 | 丰田自动车株式会社 | Catalyst for purifying exhaust gases process for producing same |
| CN101168128A (en) * | 2006-10-25 | 2008-04-30 | 刘芬 | Composite metal oxide catalyst and its preparing process and use |
| CN103758613A (en) * | 2014-01-27 | 2014-04-30 | 黄育新 | Automobile exhaust soot particle trapping burner |
-
2015
- 2015-08-27 CN CN201510534286.6A patent/CN105214649A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060793A (en) * | 1990-10-22 | 1992-05-06 | 华东化工学院 | Multieffective non-noble metal catalyst |
| JPH04267945A (en) * | 1991-02-22 | 1992-09-24 | Kazuyoshi Sugi | Catalyst furnace material for removing harmful component of exhaust gas |
| CN1141213A (en) * | 1995-07-21 | 1997-01-29 | 丰田自动车株式会社 | Catalyst for purifying exhaust gases process for producing same |
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| CN103758613A (en) * | 2014-01-27 | 2014-04-30 | 黄育新 | Automobile exhaust soot particle trapping burner |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114247448A (en) * | 2020-09-24 | 2022-03-29 | 广东加南环保生物科技有限公司 | Oxidation type catalyst for diesel engine exhaust aftertreatment and manufacturing method thereof |
| CN114247448B (en) * | 2020-09-24 | 2024-03-15 | 广东加南环保生物科技有限公司 | Oxidation catalyst for exhaust gas post-treatment of diesel engine and its manufacturing method |
| CN114029068A (en) * | 2021-12-03 | 2022-02-11 | 华设设计集团环境科技有限公司 | Catalyst for cooperative control of nitrogen oxides and particulate matters in diesel engine tail gas and preparation method and application thereof |
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Application publication date: 20160106 |