CN101690890A - Method for preparing high-thermal-stability cerium-based oxygen storage material - Google Patents
Method for preparing high-thermal-stability cerium-based oxygen storage material Download PDFInfo
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Abstract
The invention relates to a method for preparing a high-thermal-stability cerium-based oxygen storage material, which is characterized in that the cerium-based oxygen storage material comprises cerium dioxide, zirconium dioxide, aluminum oxide in a small amount and at least one rare-earth crystal stabilizer selected from lanthanum oxide, praseodymium oxide, yttrium oxide and terbium oxide. The method comprises the following steps in the preparation process: adding a proper amount of surfactant, to obtain a cerium-based composite oxide material having the characteristics of single crystalline phase, high oxygen storage performance and high specific surface area; and ageing the cerium-based composite oxide material at a high temperature (1,050 DEG C) for 5h until the specific surface area thereof is higher than 35m<2>/g and the oxygen storage capacity thereof is higher than 400 mu mol/g. According to the phase results, the cerium-based oxygen storage material has a uniform-phase structure, moreover, a uniform solid solution with a cubic fluorite structure can be prepared from zirconium dioxide, aluminum oxide, stabilizer and cerium dioxide. The preparation process of the oxygen storage material has the characteristics of simple process, lower production cost, easy industrial scale-up, etc.
Description
Relate to the field
The present invention relates to rare earth hydrogen-storing material technical field; Definitely, relate to a kind of hydrogen-storing material technology of cleaning catalyst for tail gases of automobiles, be a kind of preparation method of high-thermal-stability cerium-based oxygen storage material.
Background technology
Along with becoming increasingly conspicuous of China's urban air pollution problem; vehicle emission pollution just more and more is subjected to people's attention; The World Health Organization (WHO) and many countries (area) all adopt air quality standard to control the content of major pollutants in atmosphere, with the protection public and ecological environment.In recent ten years, because increasing sharply of automobile pollution makes China's big city pollutant discharging total of motor vehicle surpass the city of the similar scale of developed country.Simultaneously, because urban transportation and concentration of population's height, motor vehicle emission density and the pollutant levels that cause then exceed several times than developed country.In addition, because the concentration of emission height of motor-vehicle tail-gas, height of release is low, mixes in the mode of transportation of row at pedestrian, bicycle and automobile, and these waste gas are directly endangering people's physical and mental health, cause the automobile pollution problem in cities and towns very serious.
Motor-vehicle tail-gas constituent complexity, its composition mainly depends on air-fuel ratio.Mainly contain three kinds of pollutants: unburned or imperfect combustion hydrocarbon (HCs), carbon monoxide (CO) and nitrogen oxide (NOx).In addition, also have water, hydrogen, nitrogen and oxygen etc.Under any air-fuel ratio condition, tail gas is all answered allow compliance with emission standards behind catalytic purification.But only under the condition of chemical dosage ratio, the reducing agent in the tail gas and the amount of the oxidant three-way catalyst that is complementary could effectively be removed pollutant in the tail gas.Wherein, the high-performance rare-earth hydrogen-storing material is the key components of cleaning catalyst for tail gases of automobiles, the performance and the life-span of decision catalyst, be that various countries are in cleaning catalyst for tail gases of automobiles field competition focal point, the characteristics of its maximum are exactly to store oxygen under the condition of oxygen enrichment, discharge oxygen under the condition of oxygen deprivation, thereby in three-way catalyst, play a part the oxygen buffer; In addition, its effect also shows following several aspect: (1) improves the dispersion of noble metal at carrier surface, reduces the use amount of noble metal; (2) improve Al
2O
3The heat endurance of carrier; (3) the carrying out of promotion water gas shift reaction and steam reforming reaction; (4) prevent catalyst sulfur poisoning or the like.
Yet at present the subject matter that faces of cerium-based oxygen storage material is that the heat endurance of structure and texture is relatively poor under the high temperature, and specific area is lower, causes its storage/put oxygen ability drop; And texture properties such as specific area, pore volume and average pore size are important indicators weighing catalysis material performance quality, especially at the carrier that (can reach more than 1000 ℃) cleaning catalyst for tail gases of automobiles that uses under high-speed and the high temperature sometimes, more require to have high specific area, suitable pore volume and pore-size distribution.
Therefore, better for the performance that makes three-way catalyst, the present invention mainly provides a kind of hydrogen-storing material, it is characterized by to have very high thermal stability, and promptly it also keeps high specific surface area and good oxygen storage capacity under hot conditions; The preparation method is succinct simultaneously, is easy to suitability for industrialized production.
Summary of the invention
The object of the present invention is to provide a kind of preparation method with cerium-based oxygen storage material of high thermal stability, high-ratio surface and high storage oxygen performance.
The present invention is a kind of preparation method of high-thermal-stability cerium-based oxygen storage material, it is characterized in that:
The composition of high-thermal-stability cerium-based oxygen storage material contains ceria, zirconium dioxide and small amounts aluminium, and add be selected from rare earth metal lanthana, praseodymium oxide, yittrium oxide, terbium oxide wherein one or more as crystal stabilization; Wherein, the weight percentage scope of each component is: cerium oxide: 30～80%, and zirconia: 10～60%, aluminium oxide: 2～40%, rare-earth stabilizer: 2～10%;
The structure of high-thermal-stability cerium-based oxygen storage material is the homogeneous solid solution structure, and cube fluorite structure solid solution of zirconium dioxide, aluminium oxide and stabilizing agent and ceria formation homogeneous;
High-thermal-stability cerium-based oxygen storage material has following specific area before and after high temperature ageing:
(1) 600 ℃ of calcining has greater than 100m after about 3 hours
2The specific area of/g;
(2) 1050 ℃ of calcinings have greater than 35m after about 5 hours
2The specific area of/g;
High-thermal-stability cerium-based oxygen storage material has following storage oxygen performance before and after high temperature ageing:
The oxygen storage capacity of (1) 600 ℃ of calcining after about 3 hours is greater than 500 μ mol/g;
The oxygen storage capacity of (2) 1050 ℃ of calcinings after about 5 hours is greater than 400 μ mol/g;
The preparation of high-thermal-stability cerium-based oxygen storage material, be that a kind of salting liquid of cerium ion, zirconium ion and a spot of aluminum ions salting liquid and another kind of rare-earth stabilizer ion that comprises is carried out coprecipitation reaction with a kind of aqueous slkali, when coprecipitation reaction, add a kind of surfactant solution, by ageing, filtration, washing, drying, calcining, obtain having the high-thermal-stability cerium-based oxygen storage material of single crystalline phase and high storage oxygen performance, high-ratio surface and suitable pore size distribution characteristic then; Its detailed process process comprises:
(1) at ambient temperature, dissolve cerium salt, zirconates, aluminium salt and rare-earth stabilizer respectively, and be made into the nitrate solution or the carbonate solution of metal ion, be preferably the nitrate solution of metal ion by finite concentration;
(2) in above-mentioned mixing salt solution (1), add a certain proportion of surfactant solution, and fully mix a period of time; Surfactant is selected from polyethylene glycol, polyvinyl alcohol, and polyacrylamide, softex kw, hexadecyltrimethylammonium chloride is preferably polyethylene glycol or softex kw,
(3) aqueous slkali is mixed with above-mentioned (2) solution, aqueous slkali is selected from 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 or ammoniacal liquor-carbonic hydroammonium mixed solution, the pH of conditioned reaction is 7-11, then with the precipitated liquid ageing that obtains; The ageing temperature is 25～90 ℃, and digestion time is 12～48h;
(4) sediment is used the deionized water cyclic washing, after carry out drying and continue to and reach constant weight; Drying is divided into air drying or vacuum drying, and air dried temperature range is 80 to 200 ℃, is preferably 90 to 120 ℃, vacuum drying vacuum is 0.05 to 0.1MPa, temperature range is 50 to 100 ℃, and wherein preferred vacuum is 0.08MPa, and temperature is 75 ℃;
Carry out calcination processing then; Calcining is under air atmosphere, and the temperature of calcining is 500 to 700 ℃, is preferably 600 ℃, calcination time 2-4 hour, is preferably 3 hours.
Characteristics of the present invention are, adopt surfactant and the co-precipitation technology that combines, and by add surfactant in the precipitation reaction process, have weakened the interaction force between the molecule, have reached good dispersion effect, have avoided the reunion of particle and grow up; Can adopt simultaneously modes such as vacuum drying, reduce the surface tension of adsorbed water in the sample, thereby reduce contraction and the structural collapse of sediment in dry and roasting process, help to keep bigger serface and thermal stability.
The inventor has carried out XRD test (seeing accompanying drawing) to the high-thermal-stability cerium-based oxygen storage material of preparation.The result shows: the diffraction maximum that only occurs cube phase of cerium oxide in the XRD spectra, and the diffraction maximum of not having other sample occurs, this explanation is in this hydrogen-storing material, the metallic element of its contained zirconia, aluminium oxide and stabilizer oxide has entered in the lattice of cerium oxide, has formed the solid solution structure of homogeneous.
The inventor has also carried out the test of storage oxygen performance and texture property to the high-thermal-stability cerium-based oxygen storage material of preparation.Wherein measure on the ASAP 2010V4.02A type absorption instrument of specific area employing U.S. Micromeritics company, storage oxygen performance is by oxygen pulse absorption measurement.Test result shows: the cerium-based oxygen storage material of the present invention preparation has very high specific area and storage oxygen performance, wherein 600 ℃ of calcinings after about 3 hours specific area all greater than 100m
2/ g, oxygen storage capacity are all greater than 500 μ mol/g (auspicious see embodiment).Simultaneously, the present invention has also investigated the high-temperature thermal stability performance of this hydrogen-storing material, is promptly undertaken by the variation of measuring its specific area and oxygen storage capacity after the high-temperature calcination once more.Confirm that through XRD, storage oxygen performance and BET test the about 1050 ℃ of high-temperature calcinations under atmosphere of this hydrogen-storing material still have very good structural behaviour, texture property and oxygen storage capacity after about 5 hours, show that it has very high thermal stability.Its good structural stability shows that after about 5 hours, hydrogen-storing material still keeps cerium oxide cube crystal phase structure through 1050 ℃ of high-temperature calcinations, does not have other thing and occurs mutually; Texture stability shows that the specific area after the high-temperature calcination is still greater than 35m
2/ g, and keep bigger pore volume; The heat endurance of storage oxygen performance shows that through 1050 ℃ of high-temperature calcinations the oxygen storage capacity of this hydrogen-storing material all is higher than 400 μ mol/g after about 5 hours, and fall is little.Above result all can be confirmed from following embodiment.
Description of drawings
Fig. 1 is that this preparation method embodiment 1 sample compares at the XRD spectra before and after aging.
Fig. 2 is that this preparation method embodiment 2 samples compare at the XRD spectra before and after aging.
Fig. 3 is that this preparation method embodiment 3 samples compare at the XRD spectra before and after aging.
Fig. 4 is that this preparation method embodiment 4 samples compare at the XRD spectra before and after aging.
Fig. 5 is comparing at aging front and back XRD spectra of this preparation method embodiment 5 samples.
Wherein the curve in the spectrogram (1) is represented fresh sample, and roasting condition is about 3 hours of 600 ℃ of calcinings; Curve (2) expression high temperature ageing sample, aging condition is about 5 hours of 1050 ℃ of calcinings.
The specific embodiment
Provide embodiment below, 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.
Preparation consists of cerium oxide 80%, zirconia 10%, aluminium oxide 5%, the composite oxides of lanthana 5%.According to forming the amount of calculating and taking by weighing required cerous carbonate, zirconyl carbonate and aluminum nitrate, cerous carbonate, zirconyl carbonate and aluminum nitrate are placed on container, the red fuming nitric acid (RFNA) of adding 65%, the dissolving back adds an amount of deionized water fully, and mix (consumption be oxide aggregate 80%) mutually with CTAB solution, be labeled as solution 1.25wt% ammoniacal liquor is diluted, and be labeled as solution 2.Solution 1 is mixed mutually with solution 2, and adjusting pH value is about 11; Ageing 48 hours under 90 ℃ of conditions then; After filtration, after the washing, in air 110 ℃ down dry, then calcining is after 3 hours down at 600 ℃, recording its specific area by the BET method is 112m
2/ g, oxygen storage capacity are 505 μ mol/g; In 5 hours its heat endurances of post-evaluation of 1050 ℃ of temperature lower calcinations, its specific area is 35m
2/ g, oxygen storage capacity are 421 μ mol/g.
Preparation consists of cerium oxide 70%, zirconia 15%, and aluminium oxide 10%, the composite oxides of lanthana 5%, concrete preparation method is identical with method among this part embodiment 1.Institute's difference is that the pH of reaction is 9, and the ageing temperature is a room temperature.Calcining is after 2 hours down through 700 ℃, and the specific area of the fresh sample of the cerium-based oxygen storage material that obtains is 118m
2/ g, oxygen storage capacity are 515 μ mol/g; The specific area of aging back sample is 39m
2/ g, oxygen storage capacity are 410 μ mol/g.
Embodiment 3,
Preparation consists of cerium oxide 70%, zirconia 15%, and aluminium oxide 10%, the composite oxides of lanthana 5%, concrete preparation method is identical with method among this part embodiment 1.Institute's difference is that the pH of reaction is 9, and the ageing temperature is a room temperature.Calcining is after 4 hours down through 500 ℃, and the specific area of the fresh sample of the cerium-based oxygen storage material that obtains is 118m
2/ g, oxygen storage capacity are 515 μ mol/g; The specific area of aging back sample is 39m
2/ g, oxygen storage capacity are 410 μ mol/g.
Embodiment 4,
Preparation consists of cerium oxide 50%, zirconia 10%, aluminium oxide 30%, the composite oxides of lanthana 10%.Concrete preparation method is identical with method among this part embodiment 1, and institute's difference is that the pH of reaction is 7, and adopts vacuum drying.Calcining is after 3 hours down through 600 ℃, and the specific area of the fresh sample of the cerium base cerium-based oxygen storage material that obtains is 152m
2/ g, oxygen storage capacity are 536 μ mol/g; The specific area of aging back sample is 40m
2/ g, oxygen storage capacity are 428 μ mol/g.
Preparation consists of cerium oxide 40%, zirconia 50%, the composite oxides of lanthana 10%.Concrete preparation method is identical with method among this part embodiment 1, and institute's difference is that the aqueous slkali of employing is the mixed solution (mass ratio is 1: 1) of ammoniacal liquor-carbonic hydroammonium.Calcining is after 3 hours down through 600 ℃, and the specific area of the fresh sample of the cerium-based oxygen storage material that obtains is 164m
2/ g, oxygen storage capacity are 513 μ mol/g; The specific area of aging back sample is 42m
2/ g, oxygen storage capacity are 409 μ mol/g.
Claims (2)
1. the preparation method of a high-thermal-stability cerium-based oxygen storage material is characterized in that:
The composition of high-thermal-stability cerium-based oxygen storage material contains ceria, zirconium dioxide and small amounts aluminium, and add be selected from rare earth metal lanthana, praseodymium oxide, yittrium oxide, terbium oxide wherein one or more as crystal stabilization; Wherein, the weight percentage scope of each component is: cerium oxide: 30～80%, and zirconia: 10～60%, aluminium oxide: 2～40%, rare-earth stabilizer: 2～10%;
The structure of high-thermal-stability cerium-based oxygen storage material is the homogeneous solid solution structure, and cube fluorite structure solid solution of zirconium dioxide, aluminium oxide and stabilizing agent and ceria formation homogeneous;
High-thermal-stability cerium-based oxygen storage material has following specific area before and after high temperature ageing:
(1) 600 ℃ of calcining had greater than 100m after 3 hours
2The specific area of/g;
(2) 1050 ℃ of calcinings are worn out and are had greater than 35m after 5 hours
2The specific area of/g;
High-thermal-stability cerium-based oxygen storage material has following storage oxygen performance before and after high temperature ageing:
The oxygen storage capacity of (1) 600 ℃ of calcining after 3 hours is greater than 500 μ mol/g;
(2) 1050 ℃ of aging oxygen storage capacities after 5 hours of calcining are greater than 400 μ mol/g;
The preparation of high-thermal-stability cerium-based oxygen storage material, be that a kind of salting liquid of cerium ion, zirconium ion and a spot of aluminum ions salting liquid and another kind of rare-earth stabilizer ion that comprises is carried out coprecipitation reaction with a kind of aqueous slkali, when coprecipitation reaction, add a kind of surfactant solution, by ageing, filtration, washing, drying, calcining, obtain having the high-thermal-stability cerium-based oxygen storage material of single crystalline phase and high storage oxygen performance, high-ratio surface and suitable pore size distribution characteristic then; Its detailed process process comprises:
(1) at ambient temperature, dissolve cerium salt, zirconates, aluminium salt and rare-earth stabilizer respectively, and be made into the nitrate solution or the carbonate solution of metal ion by finite concentration;
(2) in above-mentioned mixing salt solution (1), add a certain proportion of surfactant solution, and fully mix a period of time; Surfactant is selected from polyethylene glycol, polyvinyl alcohol, polyacrylamide, softex kw, hexadecyltrimethylammonium chloride;
(3) aqueous slkali is mixed with above-mentioned (2) solution, aqueous slkali is selected from 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, the pH of conditioned reaction is 7-11, then with the precipitated liquid ageing that obtains; The ageing temperature is 25～90 ℃, and digestion time is 12～48h;
(4) sediment is used the deionized water cyclic washing, after carry out drying and continue to and reach constant weight; Drying is divided into air drying or vacuum drying, and air dried temperature range is 80 to 200 ℃, and vacuum drying vacuum is 0.05 to 0.1MPa, and temperature range is 50 to 100 ℃, carries out calcination processing then; Calcining is under air atmosphere, and the temperature of calcining is 400 to 700 ℃, calcination time 2-4 hour.
2. according to the preparation method of the described hydrogen-storing material of claim 1, it is characterized in that:
The preparation of high-thermal-stability cerium-based oxygen storage material, its detailed process process comprises:
(1) at ambient temperature, dissolve cerium salt, zirconates, aluminium salt and rare-earth stabilizer respectively, and be made into the nitrate solution of metal ion by finite concentration;
(2) in above-mentioned mixing salt solution (1), add a certain proportion of surfactant solution, and fully mix a period of time; Surfactant is selected from and is polyethylene glycol or softex kw;
(3) aqueous slkali is mixed with above-mentioned (2) solution, aqueous slkali is selected from and is ammonia spirit or ammoniacal liquor-carbonic hydroammonium mixed solution, and the pH of conditioned reaction is 8-9;
(4) sediment is used the deionized water cyclic washing, after carry out drying and continue to and reach constant weight; Drying is divided into air drying or vacuum drying, and air dried temperature range is 90 to 120 ℃, and vacuum drying vacuum is 0.08MPa, and temperature is 75 ℃; Carry out calcination processing then, the temperature of calcining is 600 ℃, and calcination time is 3 hours.
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| CN110292934B (en) * | 2018-03-22 | 2023-12-29 | 日本碍子株式会社 | Oxidation catalyst and method for producing same, catalyst-supporting structure, and method for producing same |
| CN110026174A (en) * | 2018-12-12 | 2019-07-19 | 四川大学 | High thermal stability CeO2-ZrO2Based oxygen storage material and preparation method thereof |
| CN111760567A (en) * | 2020-06-28 | 2020-10-13 | 江苏国盛新材料有限公司 | Cerium oxide, zirconium oxide and aluminum oxide composition with enhanced thermal stability |
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