CN101385969A - Production method and use of cerium aluminum base composite oxides material - Google Patents
Production method and use of cerium aluminum base composite oxides material Download PDFInfo
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- CN101385969A CN101385969A CNA2008102255404A CN200810225540A CN101385969A CN 101385969 A CN101385969 A CN 101385969A CN A2008102255404 A CNA2008102255404 A CN A2008102255404A CN 200810225540 A CN200810225540 A CN 200810225540A CN 101385969 A CN101385969 A CN 101385969A
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Abstract
The invention belongs to the field of inorganic composition material, and relates to a preparation method and purposes of a Ce-Al-based composite oxide material; the Ce-Al-based composite oxide material contains cerium oxide and alumina, and at least one crystal form stabilizer selected out of zirconia, lanthanum oxide, praseodymium oxide, yttria and hafnium oxide; during the preparation process, the Ce-Al-based composite oxide material with single crystal phase, high oxygen storage performance, high specific surface and suitable hole distribution characteristic is gained by adding organic template agent such as complex polyelectrolyte particles and depositing in steps; being used as the catalyst and catalyst carrier, the Ce-Al-based composite oxide material is especially applied to the fields of internal-combustion engine tail gas disposal and industrial organic waste gas.
Description
Relate to the field and the present invention relates to the inorganic composite materials technical field, definitely relate to a kind of preparation method and its usage with cerium aluminum base composite oxides material of high-ratio surface, particularly as catalyst and catalyst carrier, in the purposes that has aspect exhaust gases of internal combustion engines processing, the industrial organic exhaust gas processing.
Background technology Hyundai Motor industrial expansion has brought great traffic convenience to people, and the tail gas of motor vehicle emission has simultaneously caused huge pollution to atmosphere.Increasingly stringent along with The development in society and economy and environmental regulation, national governments have strengthened the management to automotive emission, and released one after another compression day hot gas (CNG) automobile and liquefied petroleum gas (LPG) automobile, reduced the discharge capacity of the pollutant in the tail gas, but because the continuous variation of engine operation situation, still contain imperfect combustion hydrocarbons such as methane in the tail gas, therefore need equally to purify.Cleaning catalyst for tail gases of automobiles has obtained using widely as a kind of effective pollution control means.Discover that cerium base complex rare-earth oxidate containing valuable metal material has the characteristic that absorbs oxygen under oxidizing atmosphere, discharge oxygen under reducing atmosphere, utilize effectively three kinds of oxious components in the purifying exhaust air of characteristic that this oxygen absorbs, discharges.Therefore, cerium base complex rare-earth oxidate containing valuable metal material is used as co-catalyst in a large number, has become the main flow of co-catalyst.But the present cerium base complex rare-earth oxidate containing valuable metal particle of using, the particle easy deformation is grown up in the exhaust emissions hot environment, causes reducing of specific area decline and oxygen storage volume, so directly influenced purification efficiency.Discover that in catalyst system and catalyzing, the adding of cerium oxide can suppress γ-Al
2O
3To highdensity α-Al
2O
3Phase transformation, effectively improve the stability of aluminium oxide, simultaneous oxidation aluminium also has good synergy to cerium base complex rare-earth oxidate containing valuable metal.Therefore, develop a kind of cerium aluminium base composite oxides and become new developing direction.
Summary of the invention purpose of the present invention just is being to provide a kind of preparation method with cerium aluminium base composite oxides of single crystalline phase and high-specific surface area, high storage oxygen performance and suitable pore size distribution characteristic.One of feature of this preparation method provided by the invention, be to react by fractional precipitation, and in reaction, add a kind of complex polyelectrolyte particle solution as the template agent, in order to improve the specific area and the heat resistance of the cerium aluminium base composite oxides that obtains by for example precipitation, co-precipitation or pyrohydrolysis method.
Another object of the present invention is to have developed prepared cerium aluminium base composite oxides particularly as catalyst and catalyst carrier, in the purposes that has aspect exhaust gases of internal combustion engines processing, the industrial organic exhaust gas processing.
The present invention at first relates to a kind of method for making of cerium aluminium base composite oxides, it is characterized in that:
The first step is with a kind of cerium ion and zirconium ion of comprising; Or the salting liquid of zirconium and yttrium, zirconium and lanthanum, zirconium and praseodymium, zirconium and two kinds of ions of hafnium is with a kind of precipitation reaction of aqueous slkali, when precipitation reaction, add a kind of complex polyelectrolyte particle solution as the template agent, simultaneously, adding is as the metal or the rare earth oxide of thermal stability additives, pH value after the control neutralization between 6 to 12, preferred 8 to 11; After the reaction precipitation reaction finishes, ageing under 80-95 ℃ condition, digestion time is not less than 5 hours; Making beating is standby after will precipitating ageing, filtration, washing then;
Second step was with standby slurries and contained aluminum ions salting liquid and mix in proportion, with mixed solution and a kind of aqueous slkali generation precipitation reaction, the pH value after the control neutralization between 6 to 12, preferred 8 to 11; After the reaction precipitation reaction finishes, ageing under 80-95 ℃ condition, digestion time is not less than 2 hours; To precipitate the cerium aluminium base composite oxides that obtaining after ageing, filtration, washing, drying, the calcining has single crystalline phase and high storage oxygen performance, high-specific surface area and suitable pore size distribution characteristic then;
The cerium aluminium base composite oxides that relates in the said method, its main constituent comprises cerium oxide, aluminium oxide, zirconia and thermal stability additives, and composite oxides are the solid solution structure of single crystalline phase, and the content of each constituent is, by weight percentage:
Cerium oxide: 25%-75%
Aluminium oxide: 10%-65%
Zirconia: 10%-50%
Thermal stability additives: 0%-20%;
The salting liquid of metal ion is nitrate solution, sulfate liquor and the chloride solution of metal ion in the said method, is preferably the nitrate solution of metal ion; Aqueous slkali is the mixed solution of ammonia spirit, sal volatile, ammonium bicarbonate soln, sodium carbonate liquor, sodium bicarbonate solution, sodium hydroxide solution or above any two kinds of solution; Be preferably ammonia spirit;
Complex polyelectrolyte particle as the template agent comprises: polyacrylic acid; Sodium Polyacrylate; Ammonium polyacrylate; Polyacrylamide; Softex kw; Hexadecyltrimethylammonium chloride; Poly-quaternary ammonium salt; Poly amine; Polyvinyl acetate;
Metal or rare earth oxide as thermal stability additives, the material of forming by silicon, thorium, titanium, niobium, scandium, magnesium, chromium, gallium, boron, bismuth, nickel and rare earth element, existing in compound separately or with compound mode, the amount of interpolation is to serve as to add 0 to 20% of pivot weight with cerium and Zirconium oxide;
In the said method, its process conditions comprise: drying is meant the air drying, and the baking temperature scope is 80 to 200 ℃, is preferably 90 to 120 ℃, and drying may persist to and reaches constant weight; Calcining is under air atmosphere, and the temperature range of calcining is 400 to 1200 ℃; Be preferably 500 to 800 ℃.
The invention still further relates to the purposes of the made cerium aluminium base composite oxides of above-mentioned method for making: it is characterized in that cerium aluminium base composite oxides that the present invention prepares is applicable to oxidation/reduction reaction and be that the purifying internal combustion engine tail gas of fuel is handled with gasoline, diesel oil, CNG, LPG; In these catalysis uses, the cerium aluminium base composite oxides and the noble metal of the present invention's preparation are used in combination.
The cerium aluminium base composite oxides of the present invention preparation is Powdered, can be attached on any carrier, and also can be applicable to comprise based on these compounds and have in the catalyst system and catalyzing of coating of catalytic performance, described coating is for example attached on metal integral or the ceramic-like matrix.This coating generally is to form suspension and be deposited on the carrier and obtain by this compound is mixed with carrier.
The specific area of the cerium aluminium base composite oxides of the present invention's preparation is expressed as BET, by the nitrogen absorption measurement.Investigating its heat endurance is undertaken by the variation of measuring its specific area after the high-temperature calcination once more.High-temperature calcination condition once more be under atmosphere about 1050 ℃ the calcining about 5 hours.Investigating its storage oxygen performance measures by oxygen pulse absorption.
Characteristics of the present invention are, mould plate technique and fractional precipitation have been used: by in the precipitation reaction process, adding the agent of complex polyelectrolyte particle type organic template, weakened the active force between the molecule, reached good dispersion effect, avoided the reunion of particle and grow up; Step-by-step precipitation method better is mounted in the structure of solid solution aluminium ion, the appearance of the stray crystal phase of avoiding.
Provide embodiment below the specific embodiment, the content of each constituent is all represented with the percentage by weight of corresponding oxide among the embodiment.The relevant result of specific area, storage oxygen performance lists behind example.
Embodiment 1
Preparation consists of cerium oxide 60%, aluminium oxide 30%, the composite oxides of zirconia 10%.According to forming the amount of calculating and taking by weighing required cerous carbonate, zirconyl carbonate and aluminum nitrate, cerous carbonate and zirconyl carbonate are placed on container, add 65% red fuming nitric acid (RFNA), the dissolving back adds an amount of deionized water fully, is designated as solution 1; Aluminum nitrate is added an amount of deionized water dissolving, be designated as solution 2.Adding ammoniacal liquor in solution 1 makes PH reach about 11, to precipitate 90 ℃ of ageings 48 hours, the precipitation centrifugal filtration that collection obtains makes it to separate with mother liquor, with the filter cake washing, adds water making beating back and mixes with solution 2, in mixed solution, add ammoniacal liquor and reach about 10 to PH, to precipitate 90 ℃ of ageings 12 hours, collecting precipitation also filters, washs, and is dry under 110 ℃ in air, then calcining is after 2 hours down at 600 ℃, and recording its specific area by the BET method is 110m
2/ g, oxygen storage capacity are 510mmol/g; In 5 hours its heat endurances of post-evaluation of 1050 ℃ of temperature lower calcinations, recording its specific area by the BET method is 42.3m
2/ g, oxygen storage capacity are 463mmol/g.
Embodiment 2
Preparation consists of cerium oxide 55%, aluminium oxide 30%, and zirconia 10%, the composite oxides of yittrium oxide 5%, concrete preparation method is identical with method among this part embodiment 1, and the specific area of the cerium aluminium base composite oxides fresh sample that obtains is 122m
2/ g, oxygen storage capacity are 527mmol/g; The specific area of aging back sample is 49.1m
2/ g, oxygen storage capacity are 468mmol/g.
Embodiment 3
Preparation consists of cerium oxide 55%, aluminium oxide 10%, zirconia 30%, the composite oxides of yittrium oxide 5%.Concrete preparation method is identical with method among this part embodiment 1, and the specific area of the cerium aluminium base composite oxides fresh sample that obtains is 116m
2/ g, oxygen storage capacity are 449mmol/g; The specific area of aging back sample is 45.6m
2/ g, oxygen storage capacity are 408mmol/g.
Embodiment 4
Preparation consists of cerium oxide 30%, aluminium oxide 55%, zirconia 10%, the composite oxides of yittrium oxide 5%.Concrete preparation method is identical with method among this part embodiment 1, and the specific area of the cerium aluminium base composite oxides fresh sample that obtains is 148m
2/ g, oxygen storage capacity are 444mmol/g; The specific area of aging back sample is 42.8m
2/ g, oxygen storage capacity are 430mmol/g.
Embodiment 5
Preparation consists of cerium oxide 30%, aluminium oxide 10%, zirconia 55%, the composite oxides of yittrium oxide 5%.Concrete preparation method is identical with method among this part embodiment 1, and the specific area of the cerium aluminium base composite oxides fresh sample that obtains is 113m
2/ g, oxygen storage capacity are 466mmol/g; The specific area of aging back sample is 46.3m
2/ g, oxygen storage capacity are 423mmol/g.
Claims (2)
1, a kind of method for making of cerium aluminium base composite oxides is characterized in that:
The first step is with a kind of cerium ion and zirconium ion of comprising; Or the salting liquid of zirconium and yttrium, zirconium and lanthanum, zirconium and praseodymium, zirconium and two kinds of ions of hafnium is with a kind of precipitation reaction of aqueous slkali, when precipitation reaction, add a kind of complex polyelectrolyte particle solution as the template agent, simultaneously, adding is as the metal or the rare earth oxide of thermal stability additives, pH value after the control neutralization between 6 to 12, preferred 8 to 11; After the reaction precipitation reaction finishes, ageing under 80-95 ℃ condition, digestion time is not less than 5 hours; Making beating is standby after will precipitating ageing, filtration, washing then;
Second step was with standby slurries and contained aluminum ions salting liquid and mix in proportion, with mixed solution and a kind of aqueous slkali generation precipitation reaction, the pH value after the control neutralization between 6 to 12, preferred 8 to 11; After the reaction precipitation reaction finishes, ageing under 80-95 ℃ condition, digestion time is not less than 2 hours; To precipitate the cerium aluminium base composite oxides that obtaining after ageing, filtration, washing, drying, the calcining has single crystalline phase and high storage oxygen performance, high-specific surface area and suitable pore size distribution characteristic then;
The cerium aluminium base composite oxides that relates in the said method, its main constituent comprises cerium oxide, aluminium oxide, zirconia and thermal stability additives, and composite oxides are the solid solution structure of single crystalline phase, and the content of each constituent is, by weight percentage:
Cerium oxide: 25%-75%
Aluminium oxide: 10%-65%
Zirconia: 10%-50%
Thermal stability additives: 0%-20%;
The salting liquid of metal ion is nitrate solution, sulfate liquor and the chloride solution of metal ion in the said method, is preferably the nitrate solution of metal ion; Aqueous slkali is the mixed solution of ammonia spirit, sal volatile, ammonium bicarbonate soln, sodium carbonate liquor, sodium bicarbonate solution, sodium hydroxide solution or above any two kinds of solution; Be preferably ammonia spirit;
Complex polyelectrolyte particle as the template agent comprises: polyacrylic acid; Sodium Polyacrylate; Ammonium polyacrylate; Polyacrylamide; Softex kw; Hexadecyltrimethylammonium chloride; Poly-quaternary ammonium salt; Poly amine; Polyvinyl acetate;
Metal or rare earth oxide as thermal stability additives, the material of forming by silicon, thorium, titanium, niobium, scandium, magnesium, chromium, gallium, boron, bismuth, nickel and rare earth element, existing in compound separately or with compound mode, the amount of interpolation is to serve as to add 0 to 20% of pivot weight with cerium and Zirconium oxide;
In the said method, its process conditions comprise: drying is meant the air drying, and the baking temperature scope is 80 to 200 ℃, is preferably 90 to 120 ℃, and drying may persist to and reaches constant weight; Calcining is under air atmosphere, and the temperature range of calcining is 400 to 1200 ℃; Be preferably 500 to 800 ℃.
2, according to the described method for making of claim 1, it is characterized in that the purposes of made cerium aluminium base composite oxides: the cerium aluminium base composite oxides of the present invention preparation is applicable to oxidation/reduction reaction and is that the purifying internal combustion engine tail gas of fuel is handled with gasoline, diesel oil, CNG, LPG; In these catalysis uses, the cerium aluminium base composite oxides and the noble metal of the present invention's preparation are used in combination.
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| CNA2008102255404A CN101385969A (en) | 2008-11-05 | 2008-11-05 | Production method and use of cerium aluminum base composite oxides material |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102775635A (en) * | 2012-08-16 | 2012-11-14 | 上海华明高纳稀土新材料有限公司 | Cerium hydroxide heat stabilizer and preparation method thereof |
| CN104014330A (en) * | 2014-06-10 | 2014-09-03 | 上海大学 | Mesoporous cerium-tungsten-aluminum composite oxide carrier based denitration catalyst and preparation method thereof |
| CN105249564A (en) * | 2015-11-13 | 2016-01-20 | 无锡桥阳机械制造有限公司 | Mask for preventing and treating haze |
| CN106082299A (en) * | 2016-06-28 | 2016-11-09 | 郭舒洋 | A kind of magnesium-doped, preparation method of aluminum meso-porous hollow microsphere cerium-based oxygen storage material |
| CN108947570A (en) * | 2018-09-07 | 2018-12-07 | 长沙理工大学 | A kind of porous ceramics microballoon and preparation method thereof |
| CN109569566A (en) * | 2018-12-04 | 2019-04-05 | 华微科技（苏州）有限公司 | Compound hydrogen-storing material of cerium zirconium aluminium and preparation method thereof |
| WO2019160124A1 (en) * | 2018-02-15 | 2019-08-22 | Sumitomo Chemical Company, Limited | Inorganic oxide |
| CN111939894A (en) * | 2020-09-17 | 2020-11-17 | 河北雄安稀土功能材料创新中心有限公司 | Cerium-zirconium-based composite oxide with core-shell structure and preparation method thereof |
| CN113365948A (en) * | 2019-01-29 | 2021-09-07 | 太平洋工业发展公司 | Nanocrystal-sized cerium-zirconium-aluminum oxide material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102775635A (en) * | 2012-08-16 | 2012-11-14 | 上海华明高纳稀土新材料有限公司 | Cerium hydroxide heat stabilizer and preparation method thereof |
| CN104014330A (en) * | 2014-06-10 | 2014-09-03 | 上海大学 | Mesoporous cerium-tungsten-aluminum composite oxide carrier based denitration catalyst and preparation method thereof |
| CN105249564A (en) * | 2015-11-13 | 2016-01-20 | 无锡桥阳机械制造有限公司 | Mask for preventing and treating haze |
| CN106082299A (en) * | 2016-06-28 | 2016-11-09 | 郭舒洋 | A kind of magnesium-doped, preparation method of aluminum meso-porous hollow microsphere cerium-based oxygen storage material |
| WO2019160124A1 (en) * | 2018-02-15 | 2019-08-22 | Sumitomo Chemical Company, Limited | Inorganic oxide |
| US11666889B2 (en) | 2018-02-15 | 2023-06-06 | Sumitomo Chemical Company, Limited | Inorganic oxide |
| CN108947570A (en) * | 2018-09-07 | 2018-12-07 | 长沙理工大学 | A kind of porous ceramics microballoon and preparation method thereof |
| CN109569566A (en) * | 2018-12-04 | 2019-04-05 | 华微科技（苏州）有限公司 | Compound hydrogen-storing material of cerium zirconium aluminium and preparation method thereof |
| CN113365948A (en) * | 2019-01-29 | 2021-09-07 | 太平洋工业发展公司 | Nanocrystal-sized cerium-zirconium-aluminum oxide material and preparation method thereof |
| CN111939894A (en) * | 2020-09-17 | 2020-11-17 | 河北雄安稀土功能材料创新中心有限公司 | Cerium-zirconium-based composite oxide with core-shell structure and preparation method thereof |
| WO2022057593A1 (en) * | 2020-09-17 | 2022-03-24 | 河北雄安稀土功能材料创新中心有限公司 | Cerium zirconium based composite oxide with core-shell structure and preparation method therefor |
| GB2613963A (en) * | 2020-09-17 | 2023-06-21 | Rare Earth Functional Mat Xiong An Innovation Center Co Ltd | Cerium zirconium based composite oxide with core-shell structure and preparation method therefor |
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Open date: 20090318 |