CN100396616C - High specific surface area nanometer cerium zirconium oxide preparation method - Google Patents
High specific surface area nanometer cerium zirconium oxide preparation method Download PDFInfo
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- CN100396616C CN100396616C CNB2005100017253A CN200510001725A CN100396616C CN 100396616 C CN100396616 C CN 100396616C CN B2005100017253 A CNB2005100017253 A CN B2005100017253A CN 200510001725 A CN200510001725 A CN 200510001725A CN 100396616 C CN100396616 C CN 100396616C
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Abstract
The present invention relates to a method for preparing a nanometer cerium zirconium composite oxide with a high specific surface area, which is characterized in that a salt solution with cerium ions and zirconium ions is firstly prepared; then, a surface active agent and an additive agent are added to the salt solution; the salt solution is in contact with one or more than one kind of precipitant, and the final pH value of a reaction suspension is controlled within the range of 5 to 10 to generate precipitates; then, the precipitates are filtered, washed and dried; finally, the precipitates are burnt at the temperature of 400 to 1000 DEG C to obtain a nanometer cerium zirconium composite oxide of which the specific surface area is greater than 140m<2>/g. The X-ray diffraction diagram of the cerium zirconium composite oxide prepared by the method of the present invention indicates that single solid solution with homogeneous phases is formed by the cerium zirconium composite oxide, but no simple mixed state of cerium oxide and zirconium oxide is generated. Thus, the nanometer cerium zirconium composite oxide can be used as a catalyst.
Description
One, technical field:
The present invention relates to a kind of preparation method of high specific surface area nanometer cerium zirconium oxide, belong to the preparing technical field of rare earth compound.
Two, background technology:
CeO
2Have the excellent oxygen function of storing, in cleaning catalyst for tail gases of automobiles, add CeO
2, make CO, CH
x, NO
xAll can reach effective catalyzed conversion, play the effect of three-effect catalysis.But CeO
2The oxygen ability of storing usually limitation work as CeO from the teeth outwards
2Meet high temperature, cause storing the oxygen ability drop, directly influenced the performance and the work-ing life of catalyzer owing to its specific surface area of sintering sharply reduces.ZrO
2Introducing can improve CeO
2Thermostability, with simple CeO
2Compare, cerium zirconium compound oxide has bigger oxygen ability of storing and relative high thermostability, is more suitable for using in three-way catalyst.Along with the increase of automobile pollution, the going from bad to worse of world environments, so the research of high-specific surface area cerium zirconium compound oxide preparation become the focus that people pay close attention to, so the preparation of high-specific surface area cerium zirconium compound oxide is the technology that has much practical value.
Te Kaiping 6-279027 and Te Ping open and report among the 8-16015 cerium solution and zirconium solution mixing, and add alkaline matter and obtain throw out, be 15m 1000 ℃ of roasting specific surface areas
2/ g.
Report mixes zirconium nitrate solution and cerous nitrate (IV) solution among the Chinese patent CN1193948, and mixture heats being higher than under 100 ℃ the temperature, and reaction mixture is transferred to alkalescence, obtains throw out, is 30m 900 ℃ of roasting specific surface areas
2/ g.
Joul.catal.1997 has reported the cerium zirconium compound oxide that makes with high-energy ball milling method in 169:490 ~ 502, its specific surface area is 16 ~ 20m
2/ g.
USP5747401 discloses a kind of method of utilizing the Hydrothermal Preparation cerium zirconium compound oxide, under the situation of strictness control neutralization ratio, hydro-thermal obtains precipitation, and selects to handle throw out with certain organism, the cerium zirconium compound oxide that obtains is at 900 ℃ of roasting 6hr, and specific surface area is 50m
2/ g.
In numerous methods of preparation cerium zirconium compound oxide, coprecipitation process is simple, the product homogeneity is good, is easy to suitability for industrialized production, is to prepare the most frequently used method of cerium zirconium compound oxide.
Three, summary of the invention:
The objective of the invention is to be to provide a kind of has the bigger oxygen ability of storing and have relative high thermostability, the preparation method of a kind of high specific surface area nanometer cerium zirconium oxide that is more suitable for using in three-way catalyst.
Purpose of the present invention is realized by following technical scheme: (1). the chemical molecular formula of cerium zirconium compound oxide is: Ce
1-x-yZr
xR
yO
2-δ, wherein: R is one or more other rare earth elements except that cerium, x=0.10 in the formula ~ 0.80, y=0.00 ~ 0.20;
(2). dissolve carbonate or the oxide compound of cerium or other rare earths R with a kind of acid, or make the salts solution of cerium or other rare earths R with nitrate, muriate or the vitriol of water dissolution cerium or other rare earths R; With a kind of acid dissolving zirconium carbonate, or make the salts solution of zirconium, mix the salts solution of cerium and zirconium then according to stoichiometric ratio with water dissolution Zircosol ZN, zirconyl chloride or zirconyl sulfate, and the salts solution of other rare earths R, formation metal ion salt solution A;
(3). among this salts solution A, the concentration of metal ion is 0.1 ~ 2.0mol/l, and hydrogen ion concentration is 0.001 ~ 1mol/l;
(4). add dispersion agent F in salts solution A, the add-on of dispersion agent F is 1 ~ 15% of a cerium zirconium compound oxide weight, forms solution B;
(5). in B solution, add additive T then, additive T is one or more an inorganic or organic ammonium salt compound in ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium citrate, ammonium tartrate, ammonium acetate, the Salicylate ammonium, the add-on mol ratio of additive T: M
Co/ MT=0.2 ~ 5 form solution C;
(6). it is water-soluble to get one or more precipitation agents, and precipitation agent is ammoniacal liquor, carbon ammonium, urea, alkali-metal oxyhydroxide or alkali-metal carbonate or alkali-metal acid carbonate, and making concentration is 0.05 ~ 8mol/l aqueous solution, forms solution D;
(7). solution C mixed with solution D carry out chemical reaction, the reaction times is 5 ~ 300 minutes, and the pH value of control reaction end is 5 ~ 10;
(8). the throw out that generates behind the chemical reaction is again through stirring 5 ~ 100 minutes;
(9). this throw out after filtration, washing, drying, obtain the presoma E of composite oxides;
(10). this presoma E was 400 ~ 1000 ℃ of following calcinations 2 ~ 10 hours, and its heat-up rate is per hour 50 ~ 500 ℃, promptly obtains the high specific surface area nano-cerium oxide product.
R is lanthanum, praseodymium, neodymium or yttrium.
Formed metal ion salt solution is a nitrate solution.
Dispersion agent F is one or more surfactant.
Surfactant is nonionogenic tenside or anion surfactant.
Ionic surfactant pack is drawn together: Fatty Alcohol(C12-C14 and C12-C18), polyoxyethylene glycol, polyvinyl alcohol, alcohol amide, alkylamine, alkylphenol and mix up thing.
Anion surfactant comprises: carboxylate salt, phosphoric acid salt, vitriol, sulfonate and composition thereof.
Advantage of the present invention is: adopt coprecipitation method capable of being industrialized to precipitate, step such as drying, roasting prepares high specific surface area nanometer cerium zirconium oxide, be raw material with industrial cerous carbonate, industrial carbon ammonium, industrial ammonia etc. simultaneously, be fit to suitability for industrialized production, the cost of this method is lower simultaneously.The cerium zirconium compound oxide of present method preparation has formed single homogeneous phase Solid solution, rather than cerium oxide and zirconic simple admixture, and these composite oxides can be made catalyzer and use.
Four, concrete embodiment:
Embodiment 1:
This embodiment illustrates that general formula is Ce
1-xZr
xO
2The preparation of composite oxides.
With 947gCe (NO
3)
36H
2O, 436gZr (NO
3)
45H
2O, and add the 2.78L deionized water and make solution A, add the 25g polyoxyethylene glycol therein, add the 350kg ammonium citrate again and become solution C.Get the NH of 4.22L2.1mol/L
4HCO
3Become solution D.Under condition of stirring, solution C is added drop-wise in the solution D then, in the dropping process, the pH value of solution D constantly reduces, treat that solution C drips off after, dropping ammonia solution to the pH value of reaction system is 6.5 ± 0.5; Generate white precipitate this moment, restir should precipitate 0.2 hour, with sedimentation and filtration, and with deionized water wash 3 ~ 4 times, then precipitation was placed 90 ℃ of still airs dry 12 hours, again 550 ℃ of roastings 2 hours, heat-up rate is 200 ℃/hour, product is a cerium zirconium compound oxide, and specific surface area is 154.5m
2/ g (the BET method records), it is 30～40nm that its transmission electron microscope records granularity, it is 0.296 μ m that laser particle analyzer records D50.
Embodiment 2:
This embodiment illustrates that general formula is Ce
1-x-yZr
xLa
yO
2-δThe preparation of composite oxides.
With 530g Ce (NO
3)
36H
2O, 261g Zr (NO
3)
45H
2O, 40g La (NO
3)
36H
2O and 2.31L deionized water are made solution A, add the 15g polyoxyethylene glycol therein, add 187kg ammonium sulfate again and become solution C.Get the NaHCO of 3.8L1.5mol/L
3Become solution D.Under condition of stirring, solution D is added drop-wise in the solution C then, in the dropping process, the pH value of solution C constantly increases, treat that solution D drips off after, dropping ammonia solution to the pH value of reaction system is 6.5 ± 0.5; Generate white precipitate this moment, restir should precipitate 0.4 hour, with sedimentation and filtration, and with deionized water wash 3 ~ 4 times, then precipitation was placed 120 ℃ of still airs dry 12 hours, again 500 ℃ of roastings 2 hours, heat-up rate is 150 ℃/hour, product is a composite La-Ce-Zr oxide, and specific surface area is 144.6m
2/ g (the BET method records), it is 40～50nm that its transmission electron microscope records granularity, laser particle analyzer records D
50Be 0.319 μ m.
Embodiment 3:
This embodiment illustrates that general formula is Ce
1-x-yZr
x(LaPr)
yO
2-δThe preparation of composite oxides.
With 707g Ce (NO
3)
36H
2O, 279g Zr (NO
3)
45H
2O, 53g La (NO
3)
36H
2O, 54gPr (NO
3)
36H
2O and 2.67L deionized water are made solution A,, add the 28g polyoxyethylene glycol therein, add the 297g ammonium tartrate again and become solution C.The NaOH that gets 3.5L2.Omol/L becomes solution D.Under condition of stirring, solution D is added drop-wise in the solution C then, in the dropping process, the pH value of solution C constantly increases, treat that solution D drips off after, dropping ammonia solution to the pH value of reaction system is 6.5 ± 0.5; Generate white precipitate this moment, restir should precipitate 0.2 hour, with sedimentation and filtration, and with deionized water wash 3 ~ 4 times, then precipitation was placed 120 ℃ of still airs dry 8 hours, again 450 ℃ of roastings 2 hours, heat-up rate is 200 ℃/hour, product is the La-Ce-Pr zirconium mixed oxide, and specific surface area is 158.2m
2/ g (the BET method records), it is 40～50nm that its transmission electron microscope records granularity, laser particle analyzer records D
50Be 0.376 μ m.
Embodiment 4:
This embodiment illustrates that general formula is Ce
1-x-yZr
xY
yO
2-δThe preparation of composite oxides.
With 394g Ce (NO
3)
36H
2O, 140g Zr (NO
3)
45H
2O, 14g Y (NO
3)
36H
2O and 1.67L deionized water are made solution A,, add the 16g polyoxyethylene glycol therein, add the 166g ammonium tartrate again and become solution C.Get the Na of 1.8L1.6mol/L
2(CO
3)
3Become solution D.Under condition of stirring, solution D is added drop-wise in the solution C then, in the dropping process, the pH value of solution C constantly increases, treat that solution D drips off after, dropping ammonia solution to the pH value of reaction system is 6.5 ± 0.5; Generate white precipitate this moment, restir should precipitate 0.5 hour, with sedimentation and filtration, and with deionized water wash 3 ~ 4 times, then precipitation was placed 120 ℃ of still airs dry 8 hours, again 450 ℃ of roastings 2 hours, heat-up rate is 200 ℃/hour, product is a cerium yttrium zirconium mixed oxide, and specific surface area is 162.4m
2/ g (the BET method records), it is 20～40nm that its transmission electron microscope records granularity, laser particle analyzer records D
50Be 0.205 μ m.
Claims (7)
1. the preparation method of a high specific surface area nanometer cerium zirconium oxide is characterized in that: (1). the chemical molecular formula of cerium zirconium compound oxide is: Ce
1-x-yZr
xR
yO
2-δ, wherein: R is one or more other rare earth elements except that cerium, x=0.10 in the formula ~ 0.80, y=0.00 ~ 0.20;
(2). dissolve carbonate or the oxide compound of cerium or other rare earths R with a kind of acid, or make the salts solution of cerium or other rare earths R with nitrate, muriate or the vitriol of water dissolution cerium or other rare earths R; With a kind of acid dissolving zirconium carbonate, or make the salts solution of zirconium, mix the salts solution of cerium and zirconium then according to stoichiometric ratio with water dissolution Zircosol ZN, zirconyl chloride or zirconyl sulfate, and the salts solution of other rare earths R, formation metal ion salt solution A;
(3). among this salts solution A, the concentration of metal ion is 0.1 ~ 2.0mol/l, and hydrogen ion concentration is 0.001 ~ lmol/l;
(4). add dispersion agent F in salts solution A, the add-on of dispersion agent F is 1 ~ 15% of a cerium zirconium compound oxide weight, forms solution B;
(5). in B solution, add additive T then, additive T is one or more an inorganic or organic ammonium salt compound in ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium citrate, ammonium tartrate, ammonium acetate, the Salicylate ammonium, the add-on mol ratio of additive T: M
Ce/ M
T=0.2 ~ 5, form solution C;
(6). it is water-soluble to get one or more precipitation agents, and precipitation agent is ammoniacal liquor, carbon ammonium, urea, alkali-metal oxyhydroxide or alkali-metal carbonate or alkali-metal acid carbonate, and making concentration is 0.05 ~ 8mol/l aqueous solution, forms solution D;
(7). solution C mixed with solution D carry out chemical reaction, the reaction times is 5 ~ 300 minutes, and the pH value of control reaction end is 5 ~ 10;
(8). the throw out that generates behind the chemical reaction is again through stirring 5 ~ 100 minutes;
(9). this throw out after filtration, washing, drying, obtain the presoma E of composite oxides;
(10). this presoma E was 400 ~ 1000 ℃ of following calcinations 2 ~ 10 hours, and its heat-up rate is per hour 50 ~ 500 ℃, promptly obtains the high specific surface area nano-cerium oxide product.
2. the preparation method of a kind of high specific surface area nanometer cerium zirconium oxide according to claim 1, it is characterized in that: R is lanthanum, praseodymium, neodymium or yttrium.
3. the preparation method of a kind of high specific surface area nanometer cerium zirconium oxide according to claim 1, it is characterized in that: formed metal ion salt solution is a nitrate solution.
4. the preparation method of a kind of high specific surface area nanometer cerium zirconium oxide according to claim 1, it is characterized in that: dispersion agent F is one or more surfactant.
5. the preparation method of a kind of high specific surface area nanometer cerium zirconium oxide according to claim 4, it is characterized in that: surfactant is nonionogenic tenside or anion surfactant.
6. the preparation method of a kind of high specific surface area nanometer cerium zirconium oxide according to claim 5, it is characterized in that: ionic surfactant pack is drawn together: Fatty Alcohol(C12-C14 and C12-C18), polyoxyethylene glycol, polyvinyl alcohol, alcohol amide, alkylamine, alkylphenol and mix up thing.
7. the preparation method of a kind of high specific surface area nanometer cerium zirconium oxide according to claim 5, it is characterized in that: anion surfactant comprises: carboxylate salt, phosphoric acid salt, vitriol, sulfonate and composition thereof.
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| JPWO2009075022A1 (en) * | 2007-12-10 | 2011-04-28 | 旭硝子株式会社 | Ceria-zirconia solid solution crystal fine particles and method for producing the same |
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| CN107812516B (en) * | 2017-11-09 | 2020-09-18 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of niobium pentoxide doped cerium dioxide, product and application thereof |
| CN108408757B (en) * | 2018-03-15 | 2020-06-23 | 益阳鸿源稀土有限责任公司 | Preparation method of high-purity superfine scandium oxide powder |
| CN112126977B (en) * | 2020-08-11 | 2021-11-19 | 南昌大学 | Method for preparing high-purity flaky single crystal and flaky crystal dense aggregated cerium carbonate |
| CN113996281A (en) * | 2021-11-10 | 2022-02-01 | 东北林业大学 | Method for biomimetically preparing wood-based carbon/cerium-zirconium solid solution three-way catalytic material from wood |
| CN115159557B (en) * | 2022-08-09 | 2024-01-30 | 赣州湛海新材料科技有限公司 | Preparation method of nano dysprosium oxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06279027A (en) * | 1993-02-10 | 1994-10-04 | Rhone Poulenc Chim | Composition based on mixture of zirconium oxide and cerium oxide and method for synthetic production and use thereof |
| CN1193948A (en) * | 1995-07-03 | 1998-09-23 | 罗纳·布朗克化学公司 | Composition based on zirconium oxide and cerium oxide, preparation method therefor, and use thereof |
| CN1546228A (en) * | 2003-12-12 | 2004-11-17 | 天津化工研究设计院 | Method for preparing ceria-based rare earth composite oxide material and use thereof |
-
2005
- 2005-01-18 CN CNB2005100017253A patent/CN100396616C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06279027A (en) * | 1993-02-10 | 1994-10-04 | Rhone Poulenc Chim | Composition based on mixture of zirconium oxide and cerium oxide and method for synthetic production and use thereof |
| CN1193948A (en) * | 1995-07-03 | 1998-09-23 | 罗纳·布朗克化学公司 | Composition based on zirconium oxide and cerium oxide, preparation method therefor, and use thereof |
| CN1546228A (en) * | 2003-12-12 | 2004-11-17 | 天津化工研究设计院 | Method for preparing ceria-based rare earth composite oxide material and use thereof |
Non-Patent Citations (2)
| Title |
|---|
| 铈基稀土氧化物粉体的制备及应用. 李梅等.中国稀土学报，第21卷第专辑期. 2003 |
| 铈基稀土氧化物粉体的制备及应用. 李梅等.中国稀土学报，第21卷第专辑期. 2003 * |
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