CN1264606C - Method for preparing ceria-based rare earth composite oxide material and use thereof - Google Patents
Method for preparing ceria-based rare earth composite oxide material and use thereof Download PDFInfo
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Abstract
The present invention relates to the field of inorganic composite materials, which particularly relates to a preparation method and application of a cerium-base rare earth composite oxide material. The cerium-base rare earth composite oxide material comprises cerium oxide, zirconium oxide and at least one of a lanthanum crystal form stabilizer, a praseodymium crystal form stabilizer, a yttrium crystal form stabilizer and a hafnium crystal form stabilizer. In the preparation process, a macromolecular polyelectrolyte organic template agent is added so as to obtain the cerium-base rare earth composite oxide material having the advantages of single crystal phase, high temperature stability, high specific surface area and appropriate pore distribution. The cerium-base rare earth composite oxide material can be used as a catalyst and a catalyst carrier, and especially has functions in the aspects of tail gas treatment for internal combustion engines, and industrial organic waste gas treatment.
Description
Relate to the field and the present invention relates to the inorganic composite materials technical field, the definite a kind of cerium base complex rare-earth oxidate containing valuable metal preparation methods and uses thereof that relates to high thermal stability, particularly as catalyst or catalyst carrier, in the purposes that has aspect exhaust gases of internal combustion engines processing, the industrial organic exhaust gas processing.
The background technology internal combustion engine has been discharged as mainly containing the carbon monoxide CO of harmful substances, imperfect combustion hydrocarbon HC and nitrogen oxide NO with waste gas
x, modern catalyst for treating waste gas can be converted into the major part of these harmful substances harmless composition water, carbon monoxide and nitrogen.These catalyst normally constitute uploading the co-catalyst of holding catalyst metals platinum, palladium, rhodium etc. and being used to improve its catalytic action such as catalyst carriers such as aluminium oxide, cordierites.Have as the cerium base complex rare-earth oxidate containing valuable metal material of this co-catalyst and to absorb oxygen under the oxidizing atmosphere, under reducing atmosphere, to discharge the characteristic of oxygen, 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, and its use amount increases gradually.In general, when utilizing catalyst that waste gas is handled, its treatment effeciency is directly proportional with the contact area of waste gas with activity of such catalysts, and therefore, the specific area of employed co-catalyst must be big as much as possible.But the present cerium base complex rare-earth oxidate containing valuable metal particle of using, the particle easy deformation is grown up in the gas emission hot environment, causes reducing of specific area decline and oxygen storage volume, so directly influenced exhaust purification efficiency.Thereby press for a kind of have high thermal stability and oxygen storage capacity stability; Novel cerium base complex rare-earth oxidate containing valuable metal material with improved specific area and pore size distribution characteristic.
Summary of the invention purpose of the present invention just is being to provide a kind of have high thermal stability and oxygen storage capacity stability; Preparation method with cerium base complex rare-earth oxidate containing valuable metal of improved specific area and pore size distribution characteristic.One of feature of this new method provided by the invention, be by adding a kind of complex polyelectrolyte particle solution in reaction or after the reaction, in order to improve specific area, pore property and the heat resistance of the cerium base complex rare-earth oxidate containing valuable metal that obtains by precipitation, co-precipitation or pyrohydrolysis method as the template agent.
Another object of the present invention is to have developed the purposes that prepared cerium base complex rare-earth oxidate containing valuable metal particularly has as catalyst or catalyst carrier.
Known have a variety of methods that prepare the high-ratio surface composite oxides, and they generally are divided into four basic steps: precursor synthesize, be transformed into the post processing that processing, the precursor of precursor is transformed into before the oxide composite oxides and composite oxide material.The synthetic method of preparation oxide precursor comprises: water becomes precipitation or co-precipitation, organic matter co-precipitation, spraying co-precipitation and hydrothermal technique.The present invention becomes the method for precipitation or the method for co-precipitation by water.General, the method for precipitation hydroxide hydrate is Acid-Base neutralization reaction or ion-exchange reactions in water, and often the soluble-salt that uses comprises nitrate, carbonate and halide, in and the time use general aqueous slkali commonly used.Be that example is described preparation technology's characteristics of the present invention below with the co-precipitation.
The present invention relates to a kind of preparation method of cerium base complex rare-earth oxidate containing valuable metal, it is characterized in that:
1) preparation at least aly comprises a) cerium ion in water-bearing media, and b) the soluble-salt solution mixture of zirconium ion or zirconium and yttrium, zirconium and lanthanum, zirconium and praseodymium, zirconium and two kinds of ions of hafnium; Under the situation of amount based on cerium and Zirconium oxide that adds, this ratio of expressing with cerium/atomic percent zirconium is in 1/9 to 9/1 scope; The addition of one or more in yttrium and lanthanum, praseodymium, the hafnium is based on the scope that cerium zirconium sum is 10 atomic ratio 10/0.5 to 10/3;
This mixture is obtained by dissolved solid compound in aqueous medium, or direct aqueous solution acquisition by these compounds, and the solution of determining is mixed with any order; With the mixture heating of gained, heating-up temperature is at 80 to 100 ℃, and heating process is carried out in atmosphere or in the inert gas;
2) mixture solution is heated to temperature required after, add the aqueous slkali select for use, addition is controlled at the solution pH value that makes after the neutralization between 6 to 12;
3) in neutralization reaction or after treating that neutralization reaction fully, add the complex polyelectrolyte particle as the template agent in reaction medium, the amount of interpolation is to serve as to add 1 to 5% of pivot weight with cerium and Zirconium oxide, and this process is optional under agitation carries out;
4) add metal or rare earth oxide as thermal stability additives in reaction medium, the amount of interpolation is to serve as to add 1 to 20% of pivot weight with cerium and Zirconium oxide, and this process is optional under agitation carries out;
5) after above step was finished, the ageing time of employing was 2 hours to 12 hours;
6) after ageing process is finished, from reactor, reclaim solid sediment, and adopt filtration, sedimentation or centrifugal method to separate with mother liquor,
7) sediment of Huo Deing is under atmospheric conditions, and dry under 80 to 300 ℃, drying continues to till the constant weight;
8) after dry run is finished, with the sediment calcining of reclaiming, calcining is carried out under atmosphere or inert gas atmosphere, and calcining heat is 400 to 1200 ℃, and calcination time is 1 to 4 hour;
9) preparation has high thermal stability and oxygen storage capacity stability; Cerium base complex rare-earth oxidate containing valuable metal with improved specific area and pore size distribution characteristic is Powdered, and the type of being determined on a case-by-case basis is the different particle of size, sphere, cylinder bodily form thing or honeycomb ceramics.Solubility cerium salt is cerous nitrate or cerous carbonate; The solubility zirconates is zirconium sulfate, zirconyl nitrate, basic zirconium chloride or zirconyl carbonate;
As in the yttrium of crystal stabilization and lanthanum, praseodymium, the hafnium one or more is chloride or oxide;
Aqueous slkali is selected from the mixed solution of ammonia spirit, ammonium bicarbonate soln, sodium bicarbonate solution, sodium carbonate liquor, sodium hydroxide solution or above any two kinds of solution;
Complex polyelectrolyte particle as the template agent is selected from: Sodium Polyacrylate; Polyacrylic acid; Ammonium polyacrylate; PAMC; PAMA; Non-ionic polyacrylamide; Poly-quaternary ammonium salt; Poly amine; Polyvinyl acetate;
As the metal oxide of thermal stability additives, belong to the material of forming by aluminium, silicon, thorium, titanium, niobium, scandium, magnesium, chromium, gallium, boron, bismuth, nickel and rare earth element, in compound, to exist separately or with compound mode;
Another feature of this method is that technical process is:
1) under the situation of the amount of Jia Ruing based on cerium and Zirconium oxide, this proportion of expressing with cerium/atomic percent zirconium is 2/8 to 8/2, the addition of one or more in yttrium and lanthanum, praseodymium, the hafnium is based on the scope that cerium zirconium sum is 10 atomic ratio 10/1 to 10/2.5, with the mixture heating of gained, the heating-up temperature scope is 60 to 95 ℃;
2) mixture solution is heated to temperature required after, add the aqueous slkali select for use, it is 6.5 to 10 that addition is controlled at the solution pH value scope that makes after the neutralization;
3) in neutralization reaction or after treating that neutralization reaction fully, add the complex polyelectrolyte particle as the template agent in reaction medium, the weight range of interpolation is to serve as the 2-3.5% of adding pivot weight with cerium and Zirconium oxide;
4) adding is as the metal oxide of thermal stability additives in reaction medium, and the weight range of interpolation is to serve as the 2-18% of adding pivot weight with cerium and Zirconium oxide;
5) after above step was finished, the ageing time scope of employing was 4 hours to 10 hours;
6) after dry run is finished, with the sediment calcining of reclaiming; Calcination temperature range is 500 to 800 ℃, calcination time 2 to 3 hours;
The invention still further relates to a kind of purposes of cerium base complex rare-earth oxidate containing valuable metal, it is characterized in that according to the prepared cerium base RE composite of above-described method as catalyst or catalyst carrier the purposes of handling at exhaust gases of internal combustion engines, having aspect the industrial organic exhaust gas processing.
According to the cerium base complex rare-earth oxidate containing valuable metal that method of the present invention makes, its composite oxides are single crystalline phase, and have following characteristics:
1) under atmosphere, has greater than 60m after 2 hours 600 ℃ of calcinings
2The specific area of/g and greater than the total pore volume of 0.35ml/g;
2) under atmosphere, have greater than 30m after 5 hours 1000 ℃ of calcinings
2The specific area of/g.
The cerium base complex rare-earth oxidate containing valuable metal of the present invention's preparation is applicable to various catalytic reactions, particularly oxidation/reduction reaction and exhaust gases of internal combustion engines processing.In these catalysis uses, the general and noble metal of the compound of the present invention preparation is used in combination.This compound can be attached to becoming catalyst system and catalyzing on any carrier, also can be applicable to have in the catalyst system and catalyzing of coating of catalytic performance---and described coating is attached on metal integral or ceramic-like matrix again; This coating generally is to form suspension and it is deposited on the carrier obtain by this compound is mixed with carrier.
The specific area of the cerium base complex rare-earth oxidate containing valuable metal 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 1000 ℃ the calcining 5 hours.
Inventive features of the present invention, just be to have used mould plate technique, by in the preparation process of cerium base complex rare-earth oxidate containing valuable metal, added the agent of complex polyelectrolyte particle type organic template, thereby, improved the dispersion situation of precipitation solution and deposited particles in the compound preparation, improved the crystallization crystal formation of cerium zirconium composite, and improved calcining and burnt the size and the distribution character in the aperture of missing the season down, and then the thermally conductive heat stability of compound itself when having improved catalytic purification and using, thereby the single crystalline phase and the high thermal stability that just can bring cerium base complex rare-earth oxidate containing valuable metal to have, oxygen storage capacity stability, the outstanding effect of high-specific surface area and suitable pore size distribution characteristic.
By the examples comparative of following embodiment, can show the adding of complex polyelectrolyte particle type organic template agent, for the raising of the total pore volume of made compound and once more the minimizing that descends of calcining back specific area have direct influence.
Provide embodiment below the embodiment.The relevant result of specific area, pore size distribution characteristic lists behind example.
Embodiment 1
This example is not for adding the Comparative Examples of complex polyelectrolyte particle type organic template agent.
Using the preparation of co-precipitation method to consist of cerium/atomic percent zirconium is 8/2 composite oxides.React with stoichiometric equation by cerous carbonate, zirconyl carbonate and nitric acid, and be heated to 90 ℃, and in mixed nitrate, add ammoniacal liquor and make PH reach 9, collect the precipitation centrifugal filtration that obtains and make it to separate with mother liquor, it is dry under 110 ℃ in air to obtain filter cake, ageing time 12 hours.Then calcining is after 2 hours down at 500 ℃, and recording its specific area by the BET method is 80m
2/ g, total pore volume are 0.15ml/g; In 5 hours its heat endurances of post-evaluation of 1000 ℃ of temperature lower calcinations, recording its specific area by the BET method is 12m
2/ g.
Embodiment 2
Using the preparation of co-precipitation method to consist of cerium/atomic percent zirconium is 8/2 composite oxides.React with stoichiometric equation by cerous carbonate, zirconyl carbonate and nitric acid, and be heated to 90 ℃, add ammoniacal liquor and make PH reach 9 in mixed nitrate, and add sodium polyacrylate in this process, the addition of Sodium Polyacrylate is to serve as to add 1% of pivot weight with cerium and Zirconium oxide.The precipitation centrifugal filtration that collection obtains makes it to separate with mother liquor, and it is dry under 110 ℃ in air to obtain filter cake, ageing time 12 hours.Then calcining is after 2 hours down at 500 ℃, and recording its specific area by the BET method is 85m
2/ g, total pore volume are 0.41ml/g; In 5 hours its heat endurances of post-evaluation of about 1000 ℃ of temperature lower calcinations, recording its specific area by the BET method is 29m
2/ g.
Embodiment 3
Using the preparation of co-precipitation method to consist of cerium/atomic percent zirconium is 3/7, and cerium zirconium/yttrium atom is than the composite oxides that are 10/0.5.React with stoichiometric equation by cerous nitrate, basic zirconium chloride, yittrium oxide and nitric acid, and be heated to 80 ℃, adding sodium carbonate in mixed nitrate makes PH reach 12, and in this process, adding polyacrylamide, the addition of polyacrylamide is to serve as to add 5% of pivot weight with cerium and Zirconium oxide.Add aluminium oxide, the amount of aluminium oxide is to serve as to add 20% of pivot weight with cerium and Zirconium oxide.The precipitation centrifugal filtration that collection obtains makes it to separate with mother liquor, will obtain filter cake and be dried to constant weight under 300 ℃ in air, ageing time 8 hours.Then calcining is after 1 hour down at 1200 ℃, and recording its specific area by the BET method is 70m
2/ g, total pore volume are 0.21ml/g; In 5 hours its heat endurances of post-evaluation of 1000 ℃ of temperature lower calcinations, recording its specific area by the BET method is 26m
2/ g.
Embodiment 4
Using the preparation of co-precipitation method to consist of cerium/atomic percent zirconium is 7/2, and cerium zirconium/lanthanum atomic ratio is 10/3 composite oxides.React with stoichiometric equation by cerous carbonate, zirconyl carbonate, lanthana and nitric acid, and be heated to 60 ℃, adding ammoniacal liquor in mixed nitrate makes PH reach about 7, and in this process, adding sodium polyacrylate, the addition of Sodium Polyacrylate is to serve as to add 1% of pivot weight with cerium and Zirconium oxide.Add magnesia, magnesian amount is to serve as to add 5% of pivot weight with cerium and Zirconium oxide.The collecting precipitation isolated by filtration, filter cake is dried to constant weight under 100 ℃, ageing time 4 hours.Then calcining is after 4 hours down at 500 ℃, and recording its specific area by the BET method is 80m
2/ g, total pore volume are 0.38ml/g; In 5 hours its heat endurances of post-evaluation of 1000 ℃ of temperature lower calcinations, recording its specific area by the BET method is 35m
2/ g.
Embodiment 5
Using the preparation of co-precipitation method to consist of cerium/atomic percent zirconium is 2/5, and cerium zirconium/praseodymium atomic ratio is 10/3 composite oxides.React with stoichiometric equation by cerous carbonate, basic zirconium chloride, praseodymium chloride and nitric acid, and be heated to 75 ℃, adding NaOH in mixed nitrate makes PH reach 10, and in this process, adding polyacrylamide, the addition of polyacrylamide is to serve as to add 2.5% of pivot weight with cerium and Zirconium oxide.Add silica, the amount of silica is to serve as to add 10% of pivot weight with cerium and Zirconium oxide.Filtration makes it to separate with mother liquor, and 110 ℃ of filter cakes are dry down, ageing time 4 hours, and then calcining is after 2 hours down at 800 ℃, and recording its specific area by the BET method is 80m
2/ g, total pore volume are 0.34ml/g; In 5 hours its heat endurances of post-evaluation of 1000 ℃ of temperature lower calcinations, recording its specific area is 32m
2/ g.Back four embodiment as can be known, the material that adds the complex polyelectrolyte particle formulations prepared from solutions has higher specific area and better heat endurance.
Embodiment 6
This example is the embodiment of purposes.
Be that carrier makes with the cordierite ceramic honeycomb with the preparation of embodiment 3 being matrix, is the efficient tail-gas purifying catalyst of active component with the precious metal palladium, is used for homemade certain type car tail gas clean-up, has reached European II type environmental emission standard.
Claims (3)
1. the preparation method of a cerium base complex rare-earth oxidate containing valuable metal is characterized in that:
1) preparation at least aly comprises a) cerium ion in water-bearing media, and b) the soluble-salt solution mixture of zirconium ion or zirconium and yttrium, zirconium and lanthanum, zirconium and praseodymium, zirconium and two kinds of ions of hafnium; Under the situation of amount based on cerium and Zirconium oxide that adds, this ratio of expressing with cerium/atomic percent zirconium is in 1/9 to 9/1 scope; The addition of one or more in yttrium and lanthanum, praseodymium, the hafnium is based on the scope that cerium zirconium sum is 10 atomic ratio 10/0.5 to 10/3;
This mixture is obtained by dissolved solid compound in aqueous medium, or direct aqueous solution acquisition by these compounds, and the solution of determining is mixed with any order; With the mixture heating of gained, heating-up temperature is at 80 to 100 ℃, and heating process is carried out in atmosphere or in the inert gas;
2) mixture solution is heated to temperature required after, add the aqueous slkali select for use, addition is controlled at the solution pH value that makes after the neutralization between 6 to 12;
3) in neutralization reaction or after treating that neutralization reaction fully, add the complex polyelectrolyte particle as the template agent in reaction medium, the amount of interpolation is to serve as to add 1 to 5% of pivot weight with cerium and Zirconium oxide, and this process is optional under agitation carries out;
4) add metal or rare earth oxide as thermal stability additives in reaction medium, the amount of interpolation is to serve as to add 1 to 20% of pivot weight with cerium and Zirconium oxide, and this process is optional under agitation carries out;
5) after above step was finished, the ageing time of employing was 2 hours to 12 hours;
6) after ageing process is finished, from reactor, reclaim solid sediment, and adopt filtration, sedimentation or centrifugal method to separate with mother liquor,
7) sediment of Huo Deing is under atmospheric conditions, and dry under 80 to 300 ℃, drying continues to till the constant weight;
8) after dry run is finished, with the sediment calcining of reclaiming, calcining is carried out under atmosphere or inert gas atmosphere, and calcining heat is 400 to 1200 ℃, and calcination time is 1 to 4 hour;
9) preparation has high thermal stability and oxygen storage capacity stability; Cerium base complex rare-earth oxidate containing valuable metal with improved specific area and pore size distribution characteristic is Powdered, and the type of being determined on a case-by-case basis is the different particle of size, sphere, cylinder bodily form thing or honeycomb ceramics;
Solubility cerium salt is cerous nitrate or cerous carbonate; The solubility zirconates is zirconium sulfate, zirconyl nitrate, basic zirconium chloride or zirconyl carbonate;
As in the yttrium of crystal stabilization and lanthanum, praseodymium, the hafnium one or more is chloride or oxide;
Aqueous slkali is selected from the mixed solution of ammonia spirit, ammonium bicarbonate soln, sodium bicarbonate solution, sodium carbonate liquor, sodium hydroxide solution or above any two kinds of solution;
Complex polyelectrolyte particle as the template agent is selected from: Sodium Polyacrylate; Polyacrylic acid; Ammonium polyacrylate; PAMC; PAMA; Non-ionic polyacrylamide; Poly-quaternary ammonium salt; Poly amine; Polyvinyl acetate;
As the metal oxide of thermal stability additives, belong to the material of forming by aluminium, silicon, thorium, titanium, niobium, scandium, magnesium, chromium, gallium, boron, bismuth, nickel and rare earth element, in compound, to exist separately or with compound mode.
2. in accordance with the method for claim 1, be characterised in that technical process is:
1) under the situation of the amount of Jia Ruing based on cerium and Zirconium oxide, this proportion of expressing with cerium/atomic percent zirconium is 2/8 to 8/2, the addition of one or more in yttrium and lanthanum, praseodymium, the hafnium is based on the scope that cerium zirconium sum is 10 atomic ratio 10/1 to 10/2.5, with the mixture heating of gained, the heating-up temperature scope is 60 to 95 ℃;
2) mixture solution is heated to temperature required after, add the aqueous slkali select for use, it is 6.5 to 10 that addition is controlled at the solution pH value scope that makes after the neutralization;
3) in neutralization reaction or after treating that neutralization reaction fully, add the complex polyelectrolyte particle as the template agent in reaction medium, the weight range of interpolation is to serve as the 2-3.5% of adding pivot weight with cerium and Zirconium oxide;
4) adding is as the metal oxide of thermal stability additives in reaction medium, and the weight range of interpolation is to serve as the 2-18% of adding pivot weight with cerium and Zirconium oxide;
5) after above step was finished, the ageing time scope of employing was 4 hours to 10 hours;
6) after dry run is finished, with the sediment calcining of reclaiming; Calcination temperature range is 500 to 800 ℃, calcination time 2 to 3 hours.
3. the purposes of a cerium base complex rare-earth oxidate containing valuable metal is characterized in that prepared in accordance with the method for claim 1 cerium base RE composite as catalyst or catalyst carrier, in the purposes that has aspect exhaust gases of internal combustion engines processing, the industrial organic exhaust gas processing.
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| CN100396616C (en) * | 2005-01-18 | 2008-06-25 | 内蒙古科技大学 | High specific surface area nanometer cerium zirconium oxide preparation method |
| CN100360222C (en) * | 2005-03-30 | 2008-01-09 | 四川大学 | Ce-Zr-Al based oxygen stored material and preparation method |
| FR2907444B1 (en) * | 2006-10-20 | 2008-12-19 | Rhodia Recherches & Tech | HIGH ACIDITY COMPOSITION BASED ON ZIRCONIUM OXIDES, SILICON AND AT LEAST ONE OTHER ELEMENT SELECTED FROM TITANIUM, ALUMINUM, TUNGSTEN, MOLYBDENUM, CERIUM, IRON AND MANGANESE |
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| FR2928094B1 (en) * | 2008-03-03 | 2014-07-11 | Rhodia Operations | COMPOSITION BASED ON ZIRCONIUM OXIDE, TITANIUM OXIDE OR MIXED ZIRCONIUM AND TITANIUM OXIDE ON SILICA SUPPORT, METHODS OF PREPARATION AND USE AS CATALYST |
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| CN102417352B (en) * | 2010-09-28 | 2015-02-11 | 有研稀土新材料股份有限公司 | Preparation method for zirconium-contained rare-earth composite oxide |
| JPWO2012057161A1 (en) * | 2010-10-26 | 2014-05-12 | 三井金属鉱業株式会社 | Carbon monoxide production method and production apparatus |
| CN103031438B (en) * | 2011-09-30 | 2014-08-20 | 深圳市格林美高新技术股份有限公司 | Recovery process for rare earth and noble metal in automobile tail gas purification catalyst |
| CN102765742B (en) * | 2012-07-17 | 2014-03-05 | 内蒙古科技大学 | Preparation method of cerium oxide microspheres |
| CN103409762B (en) * | 2013-07-23 | 2015-12-23 | 葛娟 | Metal detergent and preparation method thereof |
| MX2016008195A (en) * | 2013-12-23 | 2017-03-06 | Rhodia Operations | Inorganic composite oxides and methods of making the same. |
| US20160346762A1 (en) * | 2014-02-07 | 2016-12-01 | Xi'an Jiaotong University | Cerium dioxide nanoparticles and methods for their preparation and use |
| FR3050450A1 (en) * | 2016-04-26 | 2017-10-27 | Rhodia Operations | MIXED OXIDE BASED ON CERIUM AND ZIRCONIUM |
| KR20200104903A (en) * | 2018-01-08 | 2020-09-04 | 패서픽 인더스트리얼 디벨럽먼트 코퍼레이션 | Method for producing mesoporous oxygen storage material for exhaust gas treatment; the oxygen storage material and its use |
| CN109529802B (en) * | 2018-11-12 | 2021-12-28 | 山东国瓷功能材料股份有限公司 | Cerium-zirconium composite oxide and preparation method and application thereof |
| CN113544095B (en) * | 2019-03-03 | 2024-04-16 | 罗地亚经营管理公司 | Mixed oxides with high pore volume |
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