CN101797499B - Preparation method of Ce-Zr-La-O compound oxide material with high specific surface - Google Patents
Preparation method of Ce-Zr-La-O compound oxide material with high specific surface Download PDFInfo
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- CN101797499B CN101797499B CN201010116258XA CN201010116258A CN101797499B CN 101797499 B CN101797499 B CN 101797499B CN 201010116258X A CN201010116258X A CN 201010116258XA CN 201010116258 A CN201010116258 A CN 201010116258A CN 101797499 B CN101797499 B CN 101797499B
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- oxide material
- zirconium
- cerium
- lanthanum
- composite oxide
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Abstract
The invention discloses a preparation method of a Ce-Zr-La-O compound oxide material with a high specific surface, comprising the following steps of: preparing a precursor of the Ce-Zr-La-O compound oxide material by taking nitrates of Ce, Zr and La as raw materials and using a coprecipitation method and a supercritical drying method; then treating the precursor in the atmosphere of 500-600 DEG C to obtain the Ce-Zr-La-O compound oxide material, wherein the mol ratio of Ce to Zr to La is 1:(2.5-4.5):(0.155-0.235), the specific surface area of the material is more than 180 m<2>/g and the material has a mesoporous texture with the wide aperture distribution of 4-40 nm; and treating in the atmosphere of 110 DEG C, wherein the specific surface area of the treated material is more than 30 m<2>/g.
Description
Technical field
The present invention relates to the preparation method of the Ce-Zr-La-O composite oxide material of inorganic and preparation, particularly a kind of high-ratio surface that solid material is chemical.
Background technology
Automobile exhaust pollution receives much concern as a global environmental problem always.The needs of sustainable development make motor vehicle exhaust emission laws and regulations requirement increasingly stringent, and the application of catalytic conversion technique can address this problem effectively.Catalytic conversion efficiency under the air-fuel ratio condition of three-way catalyst theory is the highest, and in actual use owing to the unstability of vehicle behavior, often there is vibration by a relatively large margin in air-fuel ratio.CeO
2-ZrO
2Composite oxides can play cushioning effect to the vibration of air-fuel ratio because of having the oxygen of storing performance, thereby make three-way catalyst bring into play maximum utility as far as possible.
For catalytic performance and the CeO that improves three-way catalyst
2-ZrO
2Composite oxides store oxygen performance and heat endurance, in the cerium zirconium sosoloid system, add the CeO that other metal forms usually
2Base or ZrO
2Quito component composite oxides obtaining hydrogen-storing material with more excellent structure, texture and storage oxygen performance, thereby improve the catalytic performance of three-way catalyst, have become the focus of such new catalytic material research in this respect.At CeO
2-ZrO
2Further add other rare earth element in the composite oxides; Like rare-earth elements La, Nd, Pr etc.; Not only can significantly improve the heat endurance of composite oxides; A small amount of doping more can produce more Lattice Oxygen hole, improves the catalytic oxidization-reduction activity of flowability, oxygen storage capacity and the catalyst of body phase oxygen.At CeO
2-ZrO
2Further add an amount of transition metal in the composite oxides, generate ternary oxide with the cerium zirconium sosoloid reaction, can greatly improve the low-temperature oxidation reduction characteristic of cerium oxide, reduced the initiation temperature of catalyst like MnOx, CuO etc.In addition; As cleaning catalyst for tail gases of automobiles; Its condition of work is very harsh, and as will adapting to high-speed, resistant to elevated temperatures environment, so texture character such as the specific surface of catalyst coat material, pore volume and average pore size are being played the part of crucial role; And aspect character such as the structure of these materials, texture and storage oxygen performance depend on its preparation method to a great extent, and different preparation has remarkable influence to these character.
Summary of the invention
The technology of preparing that the purpose of this invention is to provide a kind of Ce-Zr-La-O composite oxide material of high-ratio surface.
The present invention provides the method for the Ce-Zr-La-O composite oxide material of preparation high-ratio surface; Be that nitrate with cerium, zirconium and lanthanum is raw material; Adopt coprecipitation to prepare Ce-Zr-La-O composite oxides predecessor, adopt supercritical drying dry, make the Ce-Zr-La-O composite oxide material; The mol ratio of component cerium, zirconium and lanthanum is 1: 2.5～4.5: 0.155～0.235 in the said composite oxide material, and preparation process is following:
1), be 1: 2.5～4.5: 0.155～0.235 by the mol ratio of cerium, zirconium and lanthanum, the nitrate of cerium, zirconium and lanthanum is dissolved in the water, after stirring, it is 9.0～10.0 that the pH value of dropping ammonia mixed liquor transfers to, and leaves standstill under the room temperature aging 6～12 hours;
2), the sediment that will contain cerium, zirconium and lanthanum uses the distilled water filtering and washing, again with the water in the absolute ethyl alcohol exchange sediment;
3), the sediment after the ethanol exchange is placed in the autoclave, add absolute ethyl alcohol, carry out the supercritical methanol technology drying, super critical condition is pressure 7.0～10MPa, 1.0～3.0 ℃/min of heating rate, 200～250 ℃ of temperature;
4), super critical condition kept 2～4 hours down, slowly emitted gas under the constant temperature, obtained Ce-Zr-La-O composite oxides predecessor;
5), predecessor that step 4 is obtained handles 2～4h through 500～600 ℃ in air atmosphere, make the Ce-Zr-La-O composite oxide material.
The specific area of the composite oxide material that makes according to the invention is greater than 180m
2/ g has the mesoporous texture of wide pore-size distribution 4～40nm.
The technology of preparation Ce-Zr-La-O composite oxide material provided by the present invention, its advantage is: adopt the preparation of coprecipitation and supercritical drying, technology is simple, and course of reaction is controlled easily, easy industrialization realization production; The Ce-Zr-La-O composite oxide material specific surface that makes is big, resistance to elevated temperatures good and have mesoporous texture, in 500 ℃ of air atmospheres, handles 4h like Ce-Zr-La-O composite oxides predecessor, and its specific area is greater than 180m
2/ g, and have wide pore-size distribution (4～40nm) mesoporous texture; In 1100 ℃ of air atmospheres, handle 4h, its specific area is greater than 30m
2/ g.The Ce-Zr-La-O composite oxide material of high-ratio surface of the present invention will have broad application prospects aspect the high performance cleaning catalyst for tail gases of automobiles.
The specific surface that method of the present invention has the Ce-Zr-La-O composite oxide material is big, resistance to elevated temperatures good and the characteristics of mesoporous texture.
The specific embodiment
Embodiment 1
Mol ratio by cerium, zirconium and lanthanum is: 1: 4: 0.215, the nitrate of cerium, zirconium and lanthanum is dissolved in the water, and it is 9.5 that the back dropping ammonia that stirs transfers to pH value, leaves standstill under the room temperature and wears out 10 hours.With this sediment for several times, with the water in the absolute ethyl alcohol exchange sediment, place in the autoclave then again with the distilled water filtering and washing; Add supercritical medium (ethanol); Carry out the supercritical methanol technology drying, 1.5 ℃/min of heating rate kept 2 hours after reaching 250 ℃ of temperature and pressure 8.5MPa; Slowly emit gas then under the constant temperature, obtain Ce-Zr-La-O composite oxides predecessor; This predecessor warp in air atmosphere is handled 4h for 500 ℃, resultant Ce-Zr-La-O composite oxide material, and its specific area is 202.2m
2/ g, mesoporous average pore size 18.2nm; Again the Ce-Zr-La-O composite oxide material is handled 4h in 1100 ℃ of air atmospheres, its specific area 39.6m
2/ g.
Embodiment 2
With embodiment 1 identical operations, difference is: the mol ratio of cerium, zirconium and lanthanum is changed into: 1: 4.5: 0.235.Resulting Ce-Zr-La-O composite oxides predecessor is handled 4h, the specific area 198.7m of this Ce-Zr-La-O composite oxide material in 500 ℃ of air atmospheres
2/ g, mesoporous average pore size 18.1nm; Again the Ce-Zr-La-O composite oxide material is handled 4h in 1100 ℃ of air atmospheres, its specific area 37.3m
2/ g.
Embodiment 3
With embodiment 1 identical operations, difference is: the mol ratio of cerium, zirconium and lanthanum is changed into: 1: 2.5: 0.155.Resulting Ce-Zr-La-O composite oxides predecessor is handled 4h, the specific area 190.5m of this Ce-Zr-La-O composite oxide material in 500 ℃ of air atmospheres
2/ g, mesoporous average pore size 18.8nm; Again the Ce-Zr-La-O composite oxide material is handled 4h in 1100 ℃ of air atmospheres, its specific area 32.9m
2/ g.
Embodiment 4
With embodiment 1 identical operations, difference is: supercritical temperature is changed into: 200 ℃.Resulting Ce-Zr-La-O composite oxides predecessor is handled 4h, the specific area 181.5m of this Ce-Zr-La-O composite oxide material in 500 ℃ of air atmospheres
2/ g, mesoporous average pore size 18.4nm; Again the Ce-Zr-La-O composite oxide material is handled 4h in 1100 ℃ of air atmospheres, its specific area 35.6m
2/ g.
Embodiment 5
With embodiment 1 identical operations, difference is: the sediment after the absolute ethyl alcohol exchange is placed baking oven, and 120 ℃ following dry 24 hours.Resulting Ce-Zr-La-O composite oxides predecessor is handled 4h, the specific area 169.5m of this Ce-Zr-La-O composite oxide material in 500 ℃ of air atmospheres
2/ g, mesoporous average pore size 3.6nm; Again the Ce-Zr-La-O composite oxide material is handled 4h in 1100 ℃ of air atmospheres, its specific area 25.9m
2/ g.
Claims (1)
1. the preparation method of a Ce-Zr-La-O composite oxide material; Be that nitrate with cerium, zirconium and lanthanum is raw material; Adopt coprecipitation to prepare Ce-Zr-La-O composite oxides predecessor, adopt supercritical drying dry then, make the Ce-Zr-La-O composite oxide material; The mol ratio of component cerium, zirconium and lanthanum is 1: 2.5～4.5: 0.155～0.235 in the said composite oxide material, and preparation process is:
1), be 1: 2.5～4.5: 0.155～0.235 by the mol ratio of cerium, zirconium and lanthanum, the nitrate of cerium, zirconium and lanthanum is dissolved in the water, after stirring, it is 9.0～10.0 that the pH value of dropping ammonia mixed liquor transfers to, and leaves standstill under the room temperature aging 6～12 hours;
2), the sediment that will contain cerium, zirconium and lanthanum uses the distilled water filtering and washing, again with the water in the absolute ethyl alcohol exchange sediment;
3), the sediment after the ethanol exchange is placed in the autoclave, add absolute ethyl alcohol, carry out the supercritical methanol technology drying, super critical condition is pressure 7.0～10MPa, 1.0～3.0 ℃/min of heating rate, 200～250 ℃ of temperature;
4), under super critical condition, kept 2～4 hours, slowly emit gas under the constant temperature, obtain Ce-Zr-La-O composite oxides predecessor;
5), predecessor that step 4) is obtained handled 2～4 hours through 500～600 ℃ in air atmosphere, made the Ce-Zr-La-O composite oxide material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3188829A4 (en) * | 2014-09-05 | 2018-10-31 | Neo Performance Materials (Singapore), PTE. LTD. | High porosity cerium and zirconium containing oxide |
| EP4029832A4 (en) * | 2019-09-10 | 2022-11-09 | Mitsui Mining & Smelting Co., Ltd. | Powdered complex oxide containing elemental cerium and element zirconium, exhaust gas purification catalyst composition using same, and method for producing same |
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| CN102489287B (en) * | 2011-11-11 | 2014-08-13 | 济南大学 | Preparation method of Ce-Zr-Pr-Nd-O compound oxide with high specific surface area |
| CN102744074A (en) * | 2012-07-10 | 2012-10-24 | 江苏高淳陶瓷股份有限公司 | Oxygen storage material for catalytic purification of automobile exhaust and preparation method of oxygen storage matrial |
| CN102921400A (en) * | 2012-07-24 | 2013-02-13 | 浙江大学 | Preparation method of Ce-Zr-Mg-O composite oxide oxygen-storage material |
| CN103977781B (en) * | 2014-05-27 | 2016-02-24 | 贵州大学 | A kind of preparation method of porous out-phase base catalyst and the purposes of this catalyst |
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| WO2020061723A1 (en) * | 2018-09-24 | 2020-04-02 | Rhodia Operations | Mixed oxide with improved reducibility |
| CN109433221B (en) * | 2018-11-28 | 2020-10-13 | 中国科学院过程工程研究所 | Multi-metal composite oxide catalyst, preparation method and application thereof |
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| CN100488623C (en) * | 2005-11-10 | 2009-05-20 | 北京有色金属研究总院 | Solid solution composition of cerium zirconium compound oxide with high specific surface and method for preparing the same |
| CN101433831A (en) * | 2008-12-17 | 2009-05-20 | 天津大学 | Preparation of homogeneous mischcrystal cerium-zirconium-aluminum coating material by coprecipitation method and technique thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3188829A4 (en) * | 2014-09-05 | 2018-10-31 | Neo Performance Materials (Singapore), PTE. LTD. | High porosity cerium and zirconium containing oxide |
| EP4029832A4 (en) * | 2019-09-10 | 2022-11-09 | Mitsui Mining & Smelting Co., Ltd. | Powdered complex oxide containing elemental cerium and element zirconium, exhaust gas purification catalyst composition using same, and method for producing same |
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