CN100349654C - Nano superfine micro-particle catalyst for carbon particle combustion in diesel engine tail gas and preparing method therefor - Google Patents
Nano superfine micro-particle catalyst for carbon particle combustion in diesel engine tail gas and preparing method therefor Download PDFInfo
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- CN100349654C CN100349654C CNB2004100742239A CN200410074223A CN100349654C CN 100349654 C CN100349654 C CN 100349654C CN B2004100742239 A CNB2004100742239 A CN B2004100742239A CN 200410074223 A CN200410074223 A CN 200410074223A CN 100349654 C CN100349654 C CN 100349654C
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Abstract
The present invention provides a nanometer superfine micro-particle catalyst for carbon particle combustion in diesel engine tail gas and the preparing method thereof. The catalyst is perovskite or a perovskite-like composite metal oxide composed of two or more active constituents selected from rare-earth metal, transition metal, alkali metal or alkaline earth metal. The catalyst is prepared from the active constituents by executing organic complex reaction firstly and then baking the active constituents at a high temperature. Compared with the conventional catalysts, the catalyst provided by the present invention has the advantage of high activity, and can effectively reduce the temperature of the carbon particle combustion in the discharge of the diesel engine tail gas so as to achieve the aim of purifying the discharge pollution of the diesel engine tail gas.
Description
Technical field
The present invention relates to a kind of method that reduces carbon granule ignition temperature in the diesel engine vent gas, refer in particular to a kind of perovskite (ABO that has
3) or perovskite-like (A
2BO
4) the O composite metallic oxide catalyst nano superfine micro of structure, it has higher activity than conventional catalyst, can effectively reduce the ignition temperature of the carbon granule in the exhaust emissions of diesel engine, reaches the purpose of the pollution emission of purification diesel engine.
Background technology
The fast development of Hyundai Motor industry has brought great riches to society, but the thing followed is serious exhaust emissions and noise pollution, should be along with developing of automobile industry, automobile pollution has become the primary pollution source of municipal pollution, and directly threatens human health.Diesel oil is energy-saving fuel, and the diesel engine of same power is capable of saving fuel nearlyer 25% than gasoline engine, and the diesel engine air combustion is than big, and power performance improves greatly, thereby the development diesel-motored car has become one of focus that the our times car industry pays close attention to.The characteristics of exhaust emissions of diesel engine are the oxygen content height in the tail gas, and the discharge capacity of HC, CO seldom generally has only 1/10 of gasoline engine, and discharge capacity and the gasoline engine of NOx are suitable, but the discharge capacity of carbon granule (PM) is about 30-80 times of gasoline engine.Carbon granule is to produce smell and visible dirty main cause in the auto-pollution, and its surface is absorption many organic pollutions, heavy metal element and some carcinogens usually, and the lung that deposits to the people can be detrimental to health; NOx mainly causes acid rain and chemical fumes to be polluted, so for diesel engine, the discharging that reduces nitrogen oxide (NOx) and carbon granule (PM) is to administer the key that diesel emission pollutes.Especially reduce carbon granule and more should be placed on the first place of administering the diesel emission pollution to airborne discharging.
The discharging that reduces carbon granule promptly, makes carbon granule that oxidation reaction take place as far as possible fully mainly by making the carbon granule burning convert oxycarbide to, and the effect of catalyst is very important in course of reaction.At present the problem that exists in the research that is used for eliminating the carbon granule catalyst is the oxidizing fire temperature height of carbon granule, even under carbon granule and condition that catalyst closely contacts, the ignition temperature of carbon granule also will be far above the actual exhaust air temperature of diesel engine, therefore, seek highly active catalyst, improve the contact performance of carbon granule and catalyst in the diesel engine vent gas, reducing carbon granule and the catalyst ignition temperature when loose the contact most possibly, is difficult point and the break-through point of eliminating carbon granule catalyst research in the diesel exhaust gas.In actual applications, carbon granule mainly contacts with loose with catalyst, and therefore, exploitation is under loose contact conditions, and the low-temperature combustion catalyst of carbon granule is significant.
In application number is 02136342.0 Chinese patent application, a kind of diesel exhaust gas cleaning catalyst and preparation method thereof is disclosed, its operation principle is carbon particulate (PM) reducing NOx that utilizes in the diesel engine vent gas, carbon particulate self is oxidized simultaneously, the catalyst that uses is a kind of loaded catalyst, adopts γ-Al
2O
3As carrier, utilize infusion process load active component on carrier, the active component of load is rutile-type or perofskite type oxide.Under the effect of this catalyst, the conversion ratio of NOx is at 55-70%, and the reduction of carbon granule oxidizing temperature reaches 180 ℃.But in actual applications, this is when formerly the catalyst that relates to of technology is used for eliminating the oxidation reaction of carbon granule of diesel exhaust gas, really can reach the effect of eliminating the part carbon granule, but the carbon granule oxidizing temperature that reaches is still too high, still the actual exhaust gas temperature that is higher than diesel engine vent gas can not satisfy requirement of actual application fully.
Summary of the invention
The objective of the invention is to; the catalyst of a kind of major pollutants that can be applicable in the purification diesel engine tail gas----carbon granule is provided; catalyst granules is the nano level superfine particulate; these particulates have higher surface free energy, activity and specific area; thereby has advantages of high catalytic activity; can make the carbon granule oxidizing temperature reduce (reducing by 250 ℃) significantly, in the temperature range of exhaust emissions of diesel engine, carbon granule substantially can completing combustion.
The present invention also provides the preparation method of above-mentioned nano level superfine catalyst granules.
Catalyst provided by the present invention is perovskite or the perovskite-like type composite metal oxide that is made of two or more the active component that is selected from rare earth metal, transition metal, alkali metal or the alkaline-earth metal, and this catalyst is the nano level superfine particulate.
Perovskite and perovskite-like type are more common complex metal, and perovskite-like (A
2BO
4) and perovskite (ABO
3) architectural difference of composite metal oxide is that it is by one deck perovskite (ABO
3) the stereochemical structure composite oxides that alternately constitute of structure and one deck rock salt (AO).
Inventor's result of study shows, utilize synthetic perovskite or the perovskite-like type composite metal oxide of active metal component with nanoscale particle diameter, the Stability Analysis of Structures of catalyst not only, and the specific area of catalyst is big, surface free energy and activity are big, thereby have improved the contact performance of catalyst and carbon granule.Therefore, activity of such catalysts significantly improves, and shows that the ignition temperature of carbon granule significantly reduces, and can make the carbon granule basically can completing combustion in the temperature range of exhaust emissions of diesel engine.The nano level superfine particle that the present invention mentioned should be meant the particulate of particle diameter at 1-100nm according to common understanding.
Catalyst granules of the present invention is generally the particulate of particle diameter at 2-100nm, preferably can be controlled at 20-80nm.
According to perovskite provided by the present invention or perovskite-like type O composite metallic oxide catalyst is a kind of non-precious metal catalyst, and the rare earth metal in its active component can comprise La, Nd, Pr, Sm etc.; Transition metal can comprise Fe, Co, Mn, Ni, Cu, Cr etc.; Alkali metal or alkaline-earth metal can comprise Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba etc.
Perovskite of the present invention or perovskite-like type O composite metallic oxide catalyst can be used formula Ln respectively
1-xA
xM
1-yB
yO
3And Ln
2-xA
xM
1-yB
yO
4Represent that wherein Ln is a rare earth, A is alkali metal or alkaline-earth metal, and M is a transition metal, and B is the transition metal that is different from M, and x=0-0.9, y=0-0.9.As the preferred technical solution of the present invention, the active component in the catalyst of the present invention preferably comprises a kind of rare earth metal, one or more alkali metal or alkaline-earth metal, one or more transition metal at least.
Catalyst provided by the present invention can be used for the major pollutants in the purification diesel engine tail gas----carbon granule.This catalyst is perovskite or perovskite-like type O composite metallic oxide catalyst, because its distinctive perovskite or quasi-perovskite structure and nano superfine micro, Stability Analysis of Structures, specific area is big, can effectively improve the contact performance of catalyst and carbon granule, under catalyst and the loose contact conditions of carbon granule, have very high catalytic activity, its oxidation activity to carbon granule supports precious metals pt with carbon black combustion activity the best of having reported at present under loose contact conditions
[1,2]Catalyst is suitable.Therefore, in the temperature range of exhaust emissions of diesel engine, carbon granule substantially can completing combustion.
Simultaneously, the present invention also provides the method for preparing described nanoscale perovskite or perovskite-like type O composite metallic oxide catalyst, can access high active calcium titanium ore of the present invention or perovskite-like type composite oxide catalysts by the change of concrete process conditions among the specific preparation method.
The preparation method of described perovskite or perovskite-like type O composite metallic oxide catalyst, it specifically may further comprise the steps:
1) salt that will contain described active component is mixed with the aqueous solution, mixes according to predetermined stoicheiometry, adds organic complexing agent and also mixes, and makes its burning 80-300 ℃ of following evaporating water, makes catalyst precursor;
2) with above-mentioned catalyst precursor at 400-1200 ℃ of roasting temperature 4-10 hour, can obtain perovskite or the perovskite-like type O composite metallic oxide catalyst with nano level superfine particulate of the present invention.
Preparation in accordance with the present invention adopts the organic complex method, can use conventional organic complexing agent, for example citric acid, oxalic acid, tartaric acid or urea etc.The salt that contains active component that uses should be water soluble salt, for example nitrate, acetate, chloride, carbonate etc., take by weighing according to the stoicheiometry of the active component of determining and to contain this active component salt, be mixed with the certain density aqueous solution with distilled water respectively, be the aqueous solution that this active component salt and organic complexing agent is mixed with 0.05-1.2M respectively generally speaking, and mix, wherein, organic complexing agent preferably is mixed with the aqueous solution of 0.05-0.4M.The reactant solution evaporating water also finally makes its burning, promptly makes catalyst precursor.This catalyst precursor is through roasting, can obtain needed perovskite or perovskite-like type O composite metallic oxide catalyst, the temperature and time of roasting can be controlled according to the situation of concrete component in above-mentioned scope, for example sintering temperature can 700-1000 ℃, and roasting time then can be 6-8 hour.
Diesel engine has high fuel economy and reliability, hangs down the characteristics of safeguarding cost, yet the environmental pollution that its exhaust emissions causes has seriously restricted development of diesel.Soot particle (PM) and oxynitrides (NOx) are the major pollutants of diesel engine emissions, long term studies shows, ameliorative measure is difficult to simultaneously NOx and PM are reduced to the requirement that meets strict discharge standard in the single machine, and the reproducibility of utilizing soot particle itself makes nitrogen oxide be reduced to the nitrogen of cleaning, the also oxidized carbon dioxide that burns into of while soot particle itself, catalytic purification when can realize soot particle and nitrogen oxide.On the basis of forefathers' result of study, the invention provides the nano superfine micro catalyst that adopts the preparation of organic matter complexing firing method, perovskite or perovskite-like structure have stable character, the nanocatalyst particle then has very high specific area and big surface free energy, thereby shown higher catalytic activity, when contacting with carbon granule is loose, can make the carbon granule just can oxidizing fire under the typical temperature of Diesel Engine Exhaust Pipe, improved the efficient of carbon granule combustion reaction, effectively realize the catalytic purification of PM, solved one of difficult point problem of present diesel engine pollution control.
Description of drawings
The Ca-Ti ore type La that Fig. 1 obtains for embodiment 1
0.85K
0.15CoO
3The X-ray diffraction of catalyst (XRD) figure.
Fig. 2 is that the temperature programming reaction result under contacting with carbon granule is loose with the concrete catalyst among the embodiment compares.
The Ca-Ti ore type La that Fig. 3 obtains for embodiment 3
0.85K
0.15MnO
3The ESEM of catalyst (SEM) photo figure.
The perovskite-like type La that Fig. 4 obtains for embodiment 4
1.7Rb
0.3CuO
4The X-ray diffraction spectrogram.
The perovskite-like type La that Fig. 5 obtains for embodiment 5
1.8K
0.2CuO
4The X-ray diffraction spectrogram.
The perovskite-like type La that Fig. 6 obtains for embodiment 4
1.7Rb
0.3CuO
4Amplify 20000 times SEM photo.
The specific embodiment
Below introduce realization of the present invention and the beneficial effect that had by specific embodiment, but should be not in view of the above the practical range of this case not be constituted any qualification.
The evaluation of catalyst activity:
Use fixed-bed micro-reactor-gas-chromatography detection system.Concrete method of operating is for taking by weighing the 100mg sample, and catalyst and carbon granule ratio are 10: 1, is loose contact; Gas flow is 200ml/min, and NO is 2000ppm in the gas, O
2Be 5%, remaining is He; Programming rate is 2 ℃/min.Measure the initiation temperature (T of carbon granule
Ig), the temperature (T of correspondence when burn rate is maximum
m) and after-flame temperature (T
f).
Adopt the initiation temperature (T of carbon black
Ig), the temperature (T of correspondence when burn rate is maximum
m) and after-flame temperature (T
f) assess the performance of catalytic reaction.In the carbon black catalytic combustion that we studied, the growing amount of CO is all the time less than 5%, so we have ignored the CO that reaction generates, and the CO that mainly generates with reaction
2Study the catalytic combustion of carbon black.T in this research
IgAnd T
fBe to refer to the carbon black burning CO that forms respectively
2The temperature spot that the tangent line of curve greatest gradient and the tangent line of minimum slope and zero-dose intersect, T
mBe meant CO
2Temperature spot when concentration reaches maximum (or claiming peak temperature).This mensuration process is contrast with the experimental result of catalyst-free, and its initiation temperature is higher than 420 ℃, and the temperature of correspondence was higher than 600 ℃ when burn rate was maximum, and the after-flame temperature is about 700 ℃.Structure to research catalyst adopts XRD material phase analysis method to determine; The granule size of catalyst adopts SEM and XRD to determine in conjunction with computing method.With the broadening method according to Scherrer formula D
(hkl)=0.89 λ/(β cos θ) calculates the average crystal grain size of each sample.D in the formula
(hkl)Be the crystallite dimension (nm) that causes on the normal direction of this diffraction crystal face, λ is the wavelength (nm) of irradiation targets, and θ is a glancing angle, and β is the diffraction maximum halfwidth, and unit is a radian.
Take by weighing lanthanum nitrate, potassium nitrate, cobalt nitrate and citric acid by stoichiometric proportion, they are dissolved in the deionized water, be mixed with molar concentration respectively and be 0.20,1.00,0.40 and 0.40 solution, mix then, heat evaporating water down at 100-300 ℃, and continue heating and make its sufficient combustion obtain the presoma of catalyst, 800 ℃ of following roastings 6 hours, obtain La
0.85K
0.15CoO
3The Ca-Ti ore type composite metal oxide cools off standby.
X-ray diffraction (XRD) result shows that synthetic catalyst has perovskite structure, sees Fig. 1.ESEM (SEM) is observed the pattern of its perovskite, and its granularity is about 40nm.
The catalyst activity evaluation result is under the loose condition that contacts of catalyst and carbon granule, at catalyst La
0.85K
0.15CoO
3Under the condition that exists, the ignition temperature of carbon granule reduces by 250 ℃, and initiation temperature is lower than 290 ℃, and peak temperature (Tm) is 340 ℃, and the after-flame temperature is lower than 430 ℃, sees Fig. 2.
Embodiment 2
Take by weighing lanthanum nitrate, sodium nitrate, cobalt nitrate and oxalic acid by stoichiometric proportion, they are dissolved in the deionized water, be mixed with molar concentration respectively and be 0.20,1.20,0.60 and 0.20 solution, mix then, heating evaporating water down at 100-300 ℃ makes its burning obtain the presoma of catalyst, about 8 hours of 700 ℃ of following roastings, make La
0.90Na
0.10CoO
3The perovskite type metal composite oxides cool off standby.
X-ray diffraction (XRD) result shows that synthetic catalyst is a perovskite structure, and ESEM (SEM) is observed the pattern of its perovskite, and its granularity is about 50nm.
The catalyst activity evaluation result shows, under the loose condition that contacts of catalyst and carbon granule, at catalyst La
0.90Na
0.10CoO
3Under the condition that exists, the ignition temperature of carbon granule reduces more than 250 ℃, and initiation temperature is lower than 290 ℃, and the after-flame temperature is lower than 440 ℃, sees Fig. 2.
Embodiment 3
Take by weighing lanthanum nitrate, potassium nitrate, manganese nitrate and citric acid by stoichiometric proportion, they are dissolved in the deionized water, be mixed with molar concentration respectively and be 0.20,1.00,0.20 and 0.40 solution, mix then, heating evaporating water down at 100-300 ℃ makes its burning obtain the presoma of catalyst, 900 ℃ of following roastings 6 hours, make La
0.80K
0.20MnO
3The perovskite type metal composite oxides cool off standby.
Activity rating is the result show, under the loose condition that contacts of catalyst and carbon granule, at catalyst La
0.80K
0.20MnO
3Under the condition that exists, the ignition temperature of carbon granule reduces more than 200 ℃, and initiation temperature is lower than 300 ℃, and the after-flame temperature is lower than 460 ℃, sees Fig. 2.Observe the pattern of perovskite by ESEM (SEM), see Fig. 3.Can be clear that by Fig. 3 the synthetic catalyst crystal grain of the inventive method is a nano particle, its granularity is about 60nm.
Take by weighing lanthanum nitrate, rubidium nitrate, copper nitrate and tartaric acid by stoichiometric proportion, they are dissolved in the deionized water, be mixed with molar concentration respectively and be 0.20,1.00,0.40 and 0.30 solution, mix then, heating evaporating water down at 100-300 ℃ makes its burning obtain the presoma of catalyst, 900 ℃ of following roastings 6 hours, make La
1.7Rb
0.30CuO
4Perovskite-like type composite metal oxide cools off standby.
X-ray diffraction (XRD) result (Fig. 4) shows that synthetic catalyst is a perovskite structure.ESEM (SEM) is observed the pattern (Fig. 6) of its perovskite, and its granularity is about 80nm.According to Scherrer formula D
(hkl)The grain size that=0.89 λ/(β cos θ) calculates 220 crystal faces is about 65nm.
Activity rating is the result show, under the loose condition that contacts of catalyst and carbon granule, at catalyst La
1.7Rb
0.30CuO
4Under the condition that exists, the ignition temperature of carbon granule reduces more than 210 ℃, and initiation temperature is lower than 310 ℃, and the after-flame temperature is lower than 450 ℃.
Take by weighing neodymium nitrate, copper nitrate, potassium nitrate and tartaric acid by stoichiometric proportion, they are dissolved in the deionized water, be mixed with molar concentration respectively and be 0.10,0.60,1.00 and 0.30 solution, mix then, heating evaporating water down at 100-300 ℃ makes its burning obtain the presoma of catalyst, 900 ℃ of following roastings 6 hours, make Nd
1.8K
0.20CuO
4Perovskite-like type composite metal oxide cools off standby.
X-ray diffraction (XRD) result (Fig. 5) shows that synthetic catalyst is a perovskite-like structure.ESEM (SEM) is observed the pattern of its perovskite, and its granularity is about 50-80nm.According to Scherrer formula D
(hkl)The grain size that=0.89 λ/(β cos θ) calculates 220 crystal faces is about 60nm.
Activity rating is the result show, under the loose condition that contacts of catalyst and carbon granule, at catalyst n d
1.8K
0.20CuO
4Under the condition that exists, the ignition temperature of carbon granule reduces more than 200 ℃, and initiation temperature is lower than 330 ℃, and the after-flame temperature is lower than 480 ℃.
List of references
[1]Junko?Oi-Uchisawa，Akira?Obuchi，Zhen?Zhao，Satoshi?Kushiyama.Carbonoxidation?with?platinum?supported?catalysts.Applied?Catalysis?B：Environmental，1998，18：L183-L187.
[2]Junko?Oi-Uchisawa，Akira?Obuchi，Shetian?Liu，Tesuya?Nanba，Satoshi?Kushiyama.Catalytic?performance?of?Pt?supported?on?various?metal?oxides?in?the?oxidation?of?carbonblack.Applied?Catalysis?B：Environmental，2000，26：17-24.
Claims (2)
1, reduces the method for the ignition temperature of the carbon granule in the diesel engine vent gas, it is characterized in that adopting loose contact of carbon granule in following nano level superfine catalyst particles and the diesel emission gas, heating up makes carbon granule that oxidizing fire take place under the catalysis of this catalyst to react and burn:
This catalyst particles is perovskite or the perovskite-like type composite metal oxide that is made of two or more the active component that is selected from rare earth metal, transition metal and the alkali metal, and its particle size range is 20-80nm; Rare earth metal in the described active component comprises La, Nd, Pr or Sm; Transition metal comprises Fe, Co, Mn, Ni or Cr; Alkali metal comprises Li, Na, K, Rb or Cs.
2, the described method of claim 1, wherein, described catalyst carries out after the organic complex reaction high-temperature roasting more earlier by active component and makes.
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| CN100436766C (en) * | 2006-12-06 | 2008-11-26 | 陈阳 | Catalytic purifier for motor vehicle exhaust and its preparing method and use |
| CN101468295B (en) * | 2007-12-28 | 2011-08-10 | 中国石油大学(北京) | Combined catalyst for simultaneously eliminating four kinds of pollutants from diesel exhaust and purification method |
| CN101683616B (en) * | 2008-09-28 | 2012-12-05 | 中国石油大学(北京) | Macroporous composite metal oxide catalyst for purifying soot of diesel and preparation method thereof |
| CN101733111B (en) * | 2008-11-10 | 2012-02-29 | 中国石油大学(北京) | Perovskite/cerium dioxide composite catalyst and preparation method thereof and catalytic combustion on soot |
| US8466083B2 (en) * | 2010-08-27 | 2013-06-18 | GM Global Technology Operations LLC | Bi-functional catalyst materials for lean exhaust NOx reduction |
| CN102407124A (en) * | 2011-10-21 | 2012-04-11 | 成都市翻鑫家科技有限公司 | Efficient vehicle exhaust catalyst and preparation method thereof |
| CN103372373B (en) * | 2012-04-13 | 2015-05-13 | 中国石油天然气股份有限公司 | Denitration and purification method of catalytic cracking regenerated flue gas |
| 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 |
| CN113996310B (en) * | 2021-10-22 | 2023-01-31 | 武汉工程大学 | Porous multi-doped perovskite catalyst and preparation method thereof |
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