CN101797499A - 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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- CN101797499A CN101797499A CN 201010116258 CN201010116258A CN101797499A CN 101797499 A CN101797499 A CN 101797499A CN 201010116258 CN201010116258 CN 201010116258 CN 201010116258 A CN201010116258 A CN 201010116258A CN 101797499 A CN101797499 A CN 101797499A
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- Prior art keywords
- oxide material
- cerium
- zirconium
- lanthanum
- composite oxide
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 150000001875 compounds Chemical class 0.000 title abstract 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 16
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 15
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 15
- 238000000975 co-precipitation Methods 0.000 claims abstract description 4
- 238000000352 supercritical drying Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 14
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 14
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000013049 sediment Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract 2
- 150000002823 nitrates Chemical class 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910016978 MnOx Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
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, as 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 as MnOx, CuO etc.In addition, as cleaning catalyst for tail gases of automobiles, its condition of work is very harsh, as adapting to high-speed, resistant to elevated temperatures environment, therefore the texture character such as specific surface, pore volume and average pore size of catalyst coat material 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 methods 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 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, employing supercritical drying drying, 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 described composite oxide material, and preparation process is as follows:
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), will contain the sediment distilled water filtering and washing of cerium, zirconium and lanthanum, 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 of the present 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, realizes industrialized production easily; The Ce-Zr-La-O composite oxide material specific surface that makes is big, resistance to elevated temperatures good and have mesoporous texture, handles 4h as Ce-Zr-La-O composite oxides predecessor in 500 ℃ of air atmospheres, and its specific area is greater than 180m
2/ g, and have wide pore-size distribution (4～40nm) mesoporous texture; Handle 4h in 1100 ℃ of air atmospheres, 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 distilled water filtering and washing, again with the water in the absolute ethyl alcohol exchange sediment, place in the autoclave then, 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 is handled 4h through 500 ℃ in air atmosphere, 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 the supercritical drying drying 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 described 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), will contain the sediment distilled water filtering and washing of cerium, zirconium and lanthanum, 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 (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489287A (en) * | 2011-11-11 | 2012-06-13 | 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 |
| CN103977781A (en) * | 2014-05-27 | 2014-08-13 | 贵州大学 | Preparation method of porous heterogeneous base catalyst and applications of catalyst |
| CN105481024A (en) * | 2015-11-24 | 2016-04-13 | 华北水利水电大学 | Cubic fluorite-type Y2Ce2-xCoxO7 ultrafine ceramic pigment and preparation method thereof |
| CN109433221A (en) * | 2018-11-28 | 2019-03-08 | 中国科学院过程工程研究所 | A kind of more metal composite oxide catalysts, preparation method and the usage |
| WO2020063510A1 (en) * | 2018-09-24 | 2020-04-02 | Rhodia Operations | Mixed oxide with improved reducibility |
| US10864499B2 (en) | 2014-09-05 | 2020-12-15 | Neo Performance Materials (Singapore), PTE. LTD. | High porosity cerium and zirconium containing oxide |
| CN114364460A (en) * | 2019-09-10 | 2022-04-15 | 三井金属矿业株式会社 | Powder of composite oxide containing cerium element and zirconium element, exhaust gas purifying catalyst composition using same, and method for producing same |
| CN116237035A (en) * | 2023-01-09 | 2023-06-09 | 万华化学集团电池科技有限公司 | Composite oxide propane dehydrogenation catalyst and preparation method and application thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102489287A (en) * | 2011-11-11 | 2012-06-13 | 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 |
| CN103977781A (en) * | 2014-05-27 | 2014-08-13 | 贵州大学 | Preparation method of porous heterogeneous base catalyst and applications of catalyst |
| 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 |
| US10864499B2 (en) | 2014-09-05 | 2020-12-15 | Neo Performance Materials (Singapore), PTE. LTD. | High porosity cerium and zirconium containing oxide |
| CN105481024A (en) * | 2015-11-24 | 2016-04-13 | 华北水利水电大学 | Cubic fluorite-type Y2Ce2-xCoxO7 ultrafine ceramic pigment and preparation method thereof |
| WO2020063510A1 (en) * | 2018-09-24 | 2020-04-02 | Rhodia Operations | Mixed oxide with improved reducibility |
| CN109433221A (en) * | 2018-11-28 | 2019-03-08 | 中国科学院过程工程研究所 | A kind of more metal composite oxide catalysts, preparation method and the usage |
| 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 |
| CN114364460A (en) * | 2019-09-10 | 2022-04-15 | 三井金属矿业株式会社 | Powder of composite oxide containing cerium element and zirconium element, exhaust gas purifying catalyst composition using same, and method for producing same |
| CN116237035A (en) * | 2023-01-09 | 2023-06-09 | 万华化学集团电池科技有限公司 | Composite oxide propane dehydrogenation catalyst and preparation method and application thereof |
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