CN102909023A - Automobile exhaust catalyst and preparation method thereof - Google Patents
Automobile exhaust catalyst and preparation method thereof Download PDFInfo
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- CN102909023A CN102909023A CN2012103403965A CN201210340396A CN102909023A CN 102909023 A CN102909023 A CN 102909023A CN 2012103403965 A CN2012103403965 A CN 2012103403965A CN 201210340396 A CN201210340396 A CN 201210340396A CN 102909023 A CN102909023 A CN 102909023A
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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
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- 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 invention discloses an automobile exhaust catalyst which has a chemical formula: LaxCe1-xCuO3, wherein X is 0-1. The preparation method of the automobile exhaust catalyst comprises the following steps of: (1) weighing lanthanum nitrate, cerous nitrate and copper nitrate according to the metering of the formula disclosed by claim 1; (2) fully mixing the lanthanum nitrate, cerous nitrate and copper nitrate weighed in the step (1) with a chelating agent and a solution to form a sol; and (3) drying the sol obtained in the step (2) to obtain a gel. With the adoption of the preparation method, by utilizing a metal-chelating gel method to prepare the automobile exhaust catalyst, the preparation method is simple, and the prepared product is in a perovskite structure, is high in specific surface area and has a good catalysis performance to CO gas.
Description
Technical field
The present invention relates to a kind of auto-exhaust catalyst and preparation method thereof.
Background technology
Along with the development of countries in the world economic society, the raising of people's living standard, automobile quantity sharply increases, and the scene of automobile industry is vigorous, and auto industry has also become the pillar industry of world many countries.Yet, auto industry be convenient for people to life at the development pole the earth, when improving people's quality of life, the Tail Gas that motor vehicle emission goes out has but caused more and more serious atmosphere pollution.
The pollutant of motor vehicle exhaust emission mainly is comprised of three parts: by the engine exhaust gas of blast pipe discharge, the gas of crankcase leakage and the gas (Qin Youjun, Chen Luyan, 1995) of the fuel system evaporations such as fuel tank and vaporizer.The composition of vehicle exhaust is very complicated, and 100 multiple compounds are approximately arranged, and mainly contains carbon monoxide (CO), hydrocarbon (HC), nitrogen oxide (NO
x), sulfide (SO
x), particle (lead compound, carbon black, mist of oil etc.), carbon dioxide (CO
2), formaldehyde (HCHO), methacrylaldehyde (CH
2CHCHO) etc. (Jin Xiangliang, 2007).Wherein CO, HC and NO
xTopmost composition (Liu Jurong, Song Shaofu, 2004 in the vehicle exhaust; Zou Yunhu, 1999), various countries also mainly concentrate on these several pollution sources Vehicle Emission Control.The discharging of these toxic and harmfuls, not only contaminated environment causes secondary pollution thereby also may bring out photochemical fog, even can cause acid rain, greenhouse effects and ozone cavity effect.The control automobile gas emission pollution mainly contains three kinds of measures (Fan Dinghui, 2006): measure behind measure and the machine in measure before the machine, the machine.Measure refers to that some additives of adding (such as antismoke agent) come the harmful components such as Pb in the reduce fuel oil, S, P in fuel oil before the so-called machine, or adopts unleaded gas to replace Leaded gasoline, reduces the discharge capacity of Extract from Gasoline-fueled Vehicle toxicant; Measure mainly is by changing the structure of engine, making full combustion of fuel or the part waste gas of discharge is burnt again, to reduce the harmful substance in the waste gas in the so-called machine; Measure mainly is to install catalytic converter additional behind the so-called machine, utilizes catalysis technique to accelerate CO, HC and NO in the automobile exhaust gas
xRedox reaction, make most of pollutant be converted into harmless CO
2, H
2O and N
2, reach the purpose of purifying automobile tail gas.Because the increasingly stringent of discharge standard, only depending on the interior measure of machine is impossible meet the requirements of fully.At present, all adopt three simultaneously applied general layouts of measure both at home and abroad.And cleaning catalyst for tail gases of automobiles (catalyst converter) is the main product of administering behind the car tail mechanism of qi.
The RE perovskite type cleaning catalyst for tail gases of automobiles mainly forms (Huang Zhongtao, 2004 by carrier, auxiliary agent and perovskite type rare earth complex oxide; Wang Hongxia, 2002).Wherein perovskite type rare earth complex oxide is the major catalyst that plays an important role.Nineteen fifty-two, Parravano(Parravano G, 1952) find that perovskite composite oxide can be used for the catalytic oxidation of CO.1971, Libby(Libby W.F, 1975) possibility of this compounds as auto-exhaust catalyst proposed, further studies show that ABO
3Oxidation reaction and NO to CO and HC
xReduction reaction all have certain catalytic activity, namely can use as the three-way catalyst of purifying vehicle exhaust.After this about ABO
3Research work as cleaning catalyst for tail gases of automobiles is carried out increasingly extensively.Although ABO
3CO and HC there are higher catalytic oxidation activity, but to NO
xCatalytic reduction activity high not enough.In order to improve ABO
3The three-effect catalysis performance, people attempt at B position admixture noble metal, result of study shows: as long as there is a small amount of noble metal to replace B position metal ion, just can greatly improve ABO
3Catalytic activity, and make noble metal and ABO
3Separately advantage brought into play simultaneously.Lauder(Hu Z, 1996) etc. discovery contains the ABO of Pt or Ru
3, its catalytic activity is than the ABO that does not contain noble metal
3Be significantly improved, and, to compare with noble metal catalyst, the ability that anti-Pb poisons improves greatly, thinks that noble metal replaces or the ABO of doping
3The type composite oxides are effective automotive exharst gas catalysts.Guilhaume(Guihaume N, Primet M, 1997) etc. nearest report, the ABO that noble metal replaces
3Type composite oxides LaMn
0.97Rh
0.024O
3+yThere is very high three-effect catalysis active, thinks that Rh is reductive NO
xNecessary component, and the effect of Mn ion is oxidation CO and HC.
The eighties in 20th century is to the initial stage nineties, because the shortage of Precious Metals Resources begins to consider to add rare earth abroad to cut down the consumption of noble metal in catalyst, has also launched non-noble metal research simultaneously to reduce cost.Affected by it, the research of most domestic especially contains the catalyst of the perovskite structure of rare earth with the emphasis of rare earth catalyst as exploitation, is research characteristic (Chen Huanqin, 1985 of at that time China's cleaning catalyst; Li Wan, kingly way, 1985; Wang Qiwu, Rong Jingfang, Lin Peiyan, 1980).
The perovskite type rare-earth oxide particulate should be ultrafine particle or has the micro mist of bigger serface, its preparation process has certain difficulty, the preparation method mainly contains following several: mechanical mixing, coprecipitation, sol-gel process, microemulsion method, hydrothermal synthesis method, combustion synthesis method, in the prior art, utilize the tail-gas catalyst of these method preparations, its catalytic performance often remains further to be promoted.
Summary of the invention
The purpose of this invention is to provide a kind of auto-exhaust catalyst and preparation method thereof.
The technical solution used in the present invention is:
A kind of auto-exhaust catalyst, its chemical formula is: La
xCe
1-xCuO
3, wherein, x is 0-1.
The preparation method of auto-exhaust catalyst may further comprise the steps:
1) takes by weighing lanthanum nitrate, cerous nitrate, copper nitrate;
2) lanthanum nitrate that step 1) is taken by weighing, cerous nitrate, copper nitrate fully mix to form colloidal sol with chelating agent, solvent;
3) with step 2) the colloidal sol drying of gained obtains gel and gets final product.
Described chelating agent comprises citric acid, EDTA, ammoniacal liquor, lactic acid, DNA.
The consumption of described chelating agent is 1.5-2 times of the metallic element integral molar quantity in lanthanum nitrate, cerous nitrate, three kinds of salt of copper nitrate.
The consumption of described solvent is lanthanum nitrate, cerous nitrate, copper nitrate integral molar quantity 8-10 times.
Described solvent comprises methyl alcohol, ethanol, propyl alcohol, butanols, water.
The invention has the beneficial effects as follows: the present invention utilizes the metal-chelating gel method to prepare auto-exhaust catalyst, and the preparation method is simple, and the product of making has perovskite structure, has simultaneously higher specific area, and CO gas is had preferably catalytic performance.
Description of drawings
Fig. 1 is the XRD collection of illustrative plates of catalyst series of the present invention.
Fig. 2 is that the product of test the present invention preparation is to the schematic flow sheet of the catalytic effect of CO.
The present invention is described further below in conjunction with specific embodiment:
Embodiment 1:
A kind of auto-exhaust catalyst, its chemical formula is: LaCuO
3
The preparation method of this auto-exhaust catalyst is as follows:
1) weighing of sample
According to the stoichiometric proportion of target product, with the accurate weighing lanthanum nitrate of electronic analytical balance difference, cerous nitrate, copper nitrate; While is a certain amount of citric acid of weighing also, and Citric Acid Dosage is 1.5 times of metallic element integral molar quantity.
2) precursor liquid preparation
Load weighted nitrate mixture and citric acid are added the ethanol dissolving, and the mole of ethanol is 8 times of nitrate mixture mole, stirs, and mixes;
3) preparation of colloidal sol
Precursor liquid is stirred more than 8 hours in the room temperature lower magnetic force, and gained colloidal sol is blue transparent thick liquid.
4) oven dry
Colloidal sol changed over to be put in drying box in the culture dish, dry more than the 20h for 60 ℃, get loose porous xerogel, grind into powder is for subsequent use;
5) roasting
With the previous step powder as for roasting in the program control cabinet-type electric furnace, 600 ℃ of sintering temperatures, roasting time 4h.
According to preparing La with embodiment 1 identical method
xCe
1-xCuO
3, x is respectively 0.9,0.8,0.7,0.6,0.5,0.4,0.3,0.2,0.1,0.
With LaCuO
3, La
0.9Ce
0.1CuO
3, La
0.8Ce
0.2CuO
3, La
0.7Ce
0.3CuO
3, La
0.6Ce
0.4CuO
3, La
0.5Ce
0.5CuO
3, La
0.4Ce
0.6CuO
3, La
0.3Ce
0.7CuO
3, La
0.2Ce
0.8CuO
3, La
0.1Ce
0.9CuO
3, CeCuO
3Code name is A, B, C, D, E, F, G, H, I, J, K respectively.
Test the specific area of several samples, its result such as following table:
Be the XRD collection of illustrative plates of catalyst series of the present invention such as Fig. 1.Can know that by figure sample all demonstrates the characteristic peak of perovskite structure.Along with La is partly replaced by Ce, in x≤0.5 o'clock, exist without simple metal oxide or other dephasigns in the structure of powder sample, only show single perovskite structure characteristic peak, but the increase along with x, the corresponding diffraction maximum of X ray is to high angle generation certain deviation, and certain sharpening that strengthens and narrow down occurs respective peaks intensity, and this shows that unit cell dimension is to the direction distortion that increases.When x＞0.5, perovskite structure characteristic of correspondence peak intensity weakens, and peak width broadens, have in the drawings a small amount of dephasign characteristic peak to occur, and it is more obvious to increase the dephasign characteristic peak with x, it is higher that intensity becomes, this shows the increase with x, must cause the perovskite structure distorted, keep pure ABO
3Structure, the content x of La is subject to certain restrictions.As seen from the figure, x≤0.5 o'clock can form and stoichiometric form La
xCe
1-xCuO
3Consistent single ABO
3Perovskite structure, and when x＞0.5, just have dephasign in the catalyst system, and it is more obvious to increase dephasign with x.
The product La of test the present invention preparation
0.2Ce
0.8CuO
3To the catalytic effect of CO, test flow chart as shown in Figure 2, specifically:
Allow volume ratio be the mist of the CO of 1:1 and air with the speed of 1-3ml/min the continuous powder sample La by 1g
0.2Ce
0.8CuO
3, use BaCl
2,The NaOH mixed solution absorbs the CO that is generated after the catalysis
2, the weighing mixed solution absorbs CO
2The quality of front and back calculates CO
2Thereby amount record powder sample to the catalytic performance of CO.
With said method test, the CO of generation
2Be 0.5790g, can find out, this product has preferably catalytic performance to CO.
Claims (6)
1. auto-exhaust catalyst, it is characterized in that: its chemical formula is: La
xCe
1-xCuO
3, wherein, x is 0-1.
2. the preparation method of auto-exhaust catalyst claimed in claim 1 is characterized in that: may further comprise the steps:
1) takes by weighing lanthanum nitrate, cerous nitrate, copper nitrate according to chemical formula metering claimed in claim 1;
2) lanthanum nitrate that step 1) is taken by weighing, cerous nitrate, copper nitrate fully mix to form colloidal sol with chelating agent, solvent;
3) with step 2) the colloidal sol drying of gained obtains gel and gets final product.
3. the preparation method of a kind of auto-exhaust catalyst according to claim 2, it is characterized in that: described chelating agent comprises citric acid, EDTA, ammoniacal liquor, lactic acid, DNA.
4. the preparation method of a kind of auto-exhaust catalyst according to claim 2 is characterized in that: the consumption of described chelating agent be the metallic element integral molar quantity in lanthanum nitrate, cerous nitrate, three kinds of salt of copper nitrate 1.5-2 doubly.
5. the preparation method of a kind of auto-exhaust catalyst according to claim 2 is characterized in that: the consumption of described solvent be lanthanum nitrate, cerous nitrate, copper nitrate integral molar quantity 8-10 doubly.
6. the preparation method of a kind of auto-exhaust catalyst according to claim 2, it is characterized in that: described solvent comprises methyl alcohol, ethanol, propyl alcohol, butanols, water.
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|---|---|---|---|
| CN2012103403965A CN102909023A (en) | 2012-09-14 | 2012-09-14 | Automobile exhaust catalyst and preparation method thereof |
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| CN2012103403965A CN102909023A (en) | 2012-09-14 | 2012-09-14 | Automobile exhaust catalyst and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103394345A (en) * | 2013-07-18 | 2013-11-20 | 天津大学 | Catalyst for particulate-oxidation catalytic converter of direct-injection internal combustion engine in lean-combustion cylinder |
| CN107376924A (en) * | 2017-07-17 | 2017-11-24 | 河北科技大学 | A kind of preparation method of multi-stage porous perovskite catalyst |
Citations (5)
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|---|---|---|---|---|
| JPH03118811A (en) * | 1989-10-03 | 1991-05-21 | Riken Corp | Purifying material of exhaust gas and purifying method for exhaust gas |
| CN1315920A (en) * | 1998-07-16 | 2001-10-03 | 拉瓦勒大学 | Process for synthesizing metal oxides and metal oxide having perovskite or perovskite-like crystal structure |
| CN101239313A (en) * | 2008-01-29 | 2008-08-13 | 清华大学 | Copper cerium aluminium catalyst capable of simultaneously removing carbon smoke granule and nitrogen oxide and preparation |
| 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 |
| WO2012009052A1 (en) * | 2010-07-10 | 2012-01-19 | Sumitomo Chemical Company, Limited | Process for producing olefin oxide |
-
2012
- 2012-09-14 CN CN2012103403965A patent/CN102909023A/en active Pending
Patent Citations (5)
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|---|---|---|---|---|
| JPH03118811A (en) * | 1989-10-03 | 1991-05-21 | Riken Corp | Purifying material of exhaust gas and purifying method for exhaust gas |
| CN1315920A (en) * | 1998-07-16 | 2001-10-03 | 拉瓦勒大学 | Process for synthesizing metal oxides and metal oxide having perovskite or perovskite-like crystal structure |
| CN101239313A (en) * | 2008-01-29 | 2008-08-13 | 清华大学 | Copper cerium aluminium catalyst capable of simultaneously removing carbon smoke granule and nitrogen oxide and preparation |
| 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 |
| WO2012009052A1 (en) * | 2010-07-10 | 2012-01-19 | Sumitomo Chemical Company, Limited | Process for producing olefin oxide |
Non-Patent Citations (3)
| Title |
|---|
| 《稀土》 19990225 嵇世山等 La-Ce-Cu复合金属氧化物的结构表征及催化性能 53-57 2-6 第20卷, 第01期 * |
| 嵇世山等: "La-Ce-Cu复合金属氧化物的结构表征及催化性能", 《稀土》, vol. 20, no. 01, 25 February 1999 (1999-02-25), pages 53 - 57 * |
| 嵇世山等: "La-Ce-Cu系列催化剂SO_2中毒机理研究", 《物理化学学报》, vol. 14, no. 6, 30 June 1998 (1998-06-30), pages 527 - 533 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103394345A (en) * | 2013-07-18 | 2013-11-20 | 天津大学 | Catalyst for particulate-oxidation catalytic converter of direct-injection internal combustion engine in lean-combustion cylinder |
| CN107376924A (en) * | 2017-07-17 | 2017-11-24 | 河北科技大学 | A kind of preparation method of multi-stage porous perovskite catalyst |
| CN107376924B (en) * | 2017-07-17 | 2020-12-08 | 河北科技大学 | Preparation method of hierarchical pore perovskite catalyst |
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Application publication date: 20130206 |