CN104128174A - Binary cerium-zirconium doped supported catalyst and preparation method thereof - Google Patents
Binary cerium-zirconium doped supported catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN104128174A CN104128174A CN201410395354.0A CN201410395354A CN104128174A CN 104128174 A CN104128174 A CN 104128174A CN 201410395354 A CN201410395354 A CN 201410395354A CN 104128174 A CN104128174 A CN 104128174A
- Authority
- CN
- China
- Prior art keywords
- oxide
- preparation
- carried catalyst
- cerium zirconium
- doped cerium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a solid solution, namely a supported catalyst and in particular relates to a binary cerium-zirconium doped supported catalyst. The supported catalyst comprises the following chemical components in parts by weight: 30-50 parts of cerium oxide, 30-50 parts of zirconium oxide and 1-20 parts of other rare earth oxides, wherein other rare earth oxides are at least two of lanthanum oxide, praseodymium oxide, neodymium oxide, yttrium oxide or samarium oxide. The invention also provides a preparation method of the supported catalyst. The preparation method comprises the steps of mixing all the raw materials, adding surfactants, then adjusting the pH value to 8-10 to obtain a colloidal precipitate, and roasting to obtain the product. The supported catalyst and the preparation method have the advantages that doping defects caused by doping in cerium-zirconium supports are overcome; meanwhile, the performance indexes of the supported catalyst, such as heat stability, aging specific surface area, oxygen storage capacity and the like are greatly improved; the preparation method is low in raw material price and simple in process and is beneficial to large-scale industrial production.
Description
Technical field
The present invention relates to a kind of solid solution carried catalyst, be specifically related to a kind of binary doped cerium zirconium carried catalyst and preparation method thereof.
Background technology
Cerium oxide, as a kind of important catalyst carrier, has unique oxygen storage capacity and other excellent properties.Under oxidation or reducing atmosphere, there is Ce in cerium ion
3+and Ce
4+between redox reaction, thereby realize storage oxygen and put oxygen function, contribute to realize the catalyzed conversion of vehicle exhaust etc., but at high temperature sintering very easily of pure cerium oxide, cause storing oxygen ability and decline, form cerium zirconium base oxide solid solution by the zirconium that adulterates appropriate in cerium oxide, can improve to a great extent cerium oxide high-temperature ageing resistance and store oxygen performance, therefore, get more and more people's extensive concerning round the study on the synthesis of cerium zirconium base oxide solid solution.But there is the defects such as production cost is high, powder reuniting is serious, specific area is little in existing cerium oxide carrying body catalyst.
Summary of the invention
For the deficiencies in the prior art, the object of this invention is to provide a kind of binary doped cerium zirconium carried catalyst, overcome the doping defect of adulterating produced in cerium zirconium carrier, greatly improved the performance indications such as heat endurance and aging specific area, oxygen storage capacity of carried catalyst simultaneously; The present invention also provides its preparation method, and cost of material is cheap, and technical process is simple, is conducive to large-scale industrialization and produces.
Binary doped cerium zirconium carried catalyst of the present invention, chemical composition composition and weight content are:
Cerium oxide 30-50 part, zirconia 30-50 part and other rare earth oxide 1-20 part;
Wherein, other rare earth oxide is: in lanthana, praseodymium oxide, neodymia, yittrium oxide or samarium oxide at least two kinds.
Preferred chemical composition composition and weight content are:
Cerium oxide 30-50 part, zirconia 30-50 part, lanthana 0.5-1 part, praseodymium oxide 0.5-1 part, neodymia 2-3 part, yittrium oxide 3-4 part and samarium oxide 5-8 part.
Other rare earth oxide that adulterates in cerium zirconium carrier can improve its specific area and oxygen storage capacity, especially when samaria doped, the oxygen storage capacity of depositing of catalyst has had very large improvement, in the time of samaria doped in carried catalyst, in low doping concentration scope, along with the increase of doping oxide concentration, the oxygen storage capacity of depositing of carried catalyst has rising trend, but in high concentration range, along with the further increase of doping oxide concentration, carried catalyst deposit oxygen storage capacity and high-temperature stability step-down on the contrary, cerium oxide 30-50 part, when zirconia 30-50 part, samarium oxide preferably adds samarium oxide 5-8 part, within the scope of this carried catalyst deposit oxygen storage capacity and high-temperature stability is the strongest.In cerium zirconium carrier, adulterate and must overcome the generation of doping defect, because introduce low price (or high price) cation oxide in cerium zirconium crystal time, when cation occupies the lattice position of quadrivalent cerium ion, produce defect for the balance of retaining zone electric charge.And selective oxidation lanthanum 0.5-1 part of the present invention, praseodymium oxide 0.5-1 part, neodymia 2-3 part, yittrium oxide 3-4 part and samarium oxide 5-8 part are added in cerium oxide 30-50 part and zirconia 30-50 part jointly, overcome significantly the generation of doping defect.
The preparation method of described binary doped cerium zirconium carried catalyst, comprises the following steps:
(1) aqueous solution of salt corresponding to cerium chloride, zirconium nitrate and other rare earth oxide is obtained to mixed liquor, the concentration of mixed liquor is controlled at 0.4-0.5mol/L, and material liquid pH value is controlled between 1-3, stirs;
(2) add the surfactant for the 0.1-1% of mixed liquor of weight fraction, after stirring, be placed on and in thermostat, leave standstill 1-2 hour;
(3) under room temperature state, ammoniacal liquor or NaOH are added in the feed liquid obtaining in step (2), control pH value between 8-10, can obtain a kind of gelatinous precipitate;
(4) the gelatinous precipitate deionized water obtaining in step (3) is washed and dewatered;
(5) product dehydration in step (4) being obtained is put in kiln roasting 4-6 hour under 500-700 DEG C of condition, after then pulverizing, obtains described binary doped cerium zirconium carried catalyst.
Wherein:
The salt that in step (1), other rare earth oxide is corresponding is its corresponding chlorate or nitrate.
The pH of step (1) feed liquid is by adding ammoniacal liquor, carbonic hydroammonium or NaOH adjustment.
Surfactant described in step (2) is non-ionic surface active agent or anion surfactant.
Non-ionic surface active agent is one or more in polyethylene glycols, oleic acid or alkyl amine.
Anion surfactant is one or more in phosphate or sulfonate.
In step (2), the temperature constant of thermostat is at 40-50 DEG C.
Particle diameter after pulverizing in step (5) is 1-5 micron.
In sum, the present invention has the following advantages:
(1) by optimizing component and content, overcome the doping defect of adulterating produced in cerium zirconium carrier.
(2) the present invention improves the performance indications such as heat endurance and aging specific area, oxygen storage capacity of carried catalyst greatly, the carried catalyst preparing is to exist with solid solution form, its grain size is: 1-10nm, the fresh specific area through 500-700 DEG C of calcining after 4-6 hour is: 150-180m
2/ g, 1000 DEG C calcining 10 hours after aging specific area be: 50-80m
2/ g, oxygen storage capacity is higher than 1000umol/g.
(3) cost of material is cheap, and technical process is simple, is conducive to large-scale industrialization and produces.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
Prepare a kind of first doped with cerium zirconium carried catalyst, chemical composition composition and weight content are:
5 parts of 30 parts of cerium oxide, 30 parts of zirconias, 0.5 part of lanthana, 0.5 part of praseodymium oxide, 2 parts of neodymia, 3 parts of yittrium oxide and samarium oxides.
Preparation method comprises the following steps:
(1) cerium chloride, zirconium nitrate, lanthanum chloride, praseodymium chloride, neodymium chloride, yttrium chloride, samarium trichloride are mixed to get to mixed liquor, the concentration of mixed liquor is controlled at 0.45mol/L, adds ammoniacal liquor and regulates material liquid pH value to be controlled at 2, stirs;
(2) add 0.5% the surfactant (polyethylene glycol) for mixed liquor of weight fraction, be placed in thermostat and leave standstill 1.5 hours after stirring, the temperature constant of thermostat is at 45 DEG C;
(3) under room temperature state, ammoniacal liquor is added in the feed liquid obtaining in step (2), control pH value 9, can obtain a kind of gelatinous precipitate;
(4) the gelatinous precipitate deionized water obtaining in step (3) is washed and dewatered;
(5) product dehydration in step (4) being obtained is put in kiln under 600 DEG C of conditions roasting 5 hours, and being then crushed to particle diameter is 3 microns, obtains described binary doped cerium zirconium carried catalyst.
The grain size of the carried catalyst that embodiment 1 prepares is: 5nm, the fresh specific area through 500-700 DEG C of calcining after 6 hours is: 180m
2/ g, 1000 DEG C calcining 10 hours after aging specific area be: 80m
2/ g, oxygen storage capacity is 1660umol/g.
Embodiment 2
Prepare a kind of binary doped cerium zirconium carried catalyst, chemical composition composition and weight content are:
7 parts of 50 parts of cerium oxide, 50 parts of zirconias, 1 part of lanthana, 0.7 part of praseodymium oxide, 2.5 parts of neodymia, 3.5 parts of yittrium oxide and samarium oxides.
Preparation method comprises the following steps:
(1) cerium chloride, zirconium nitrate, lanthanum chloride, praseodymium chloride, neodymium chloride, yttrium chloride, samarium trichloride are mixed to get to mixed liquor, the concentration of mixed liquor is controlled at 0.4mol/L, adds carbonic hydroammonium and regulates material liquid pH value to be controlled at 1, stirs;
(2) add 0.1% the surfactant (oleic acid) for mixed liquor of weight fraction, be placed in thermostat and leave standstill 2 hours after stirring, the temperature constant of thermostat is at 40 DEG C;
(3) under room temperature state, NaOH is added in the feed liquid obtaining in step (2), control pH value 10, can obtain a kind of gelatinous precipitate;
(4) the gelatinous precipitate deionized water obtaining in step (3) is washed and dewatered;
(5) product dehydration in step (4) being obtained is put in kiln under 500 DEG C of conditions roasting 6 hours, and being then crushed to particle diameter is 1 micron, obtains described binary doped cerium zirconium carried catalyst.
The grain size of the carried catalyst that embodiment 2 prepares is: 8nm, the fresh specific area through 500-700 DEG C of calcining after 6 hours is: 160m
2/ g, 1000 DEG C calcining 10 hours after aging specific area be: 75m
2/ g, oxygen storage capacity is 1400umol/g.
Embodiment 3
Prepare a kind of binary doped cerium zirconium carried catalyst, chemical composition composition and weight content are:
8 parts of 40 parts of cerium oxide, 45 parts of zirconias, 0.8 part of lanthana, 1 part of praseodymium oxide, 3 parts of neodymia, 4 parts of yittrium oxide and samarium oxides.
Preparation method comprises the following steps:
(1) cerium chloride, zirconium nitrate, lanthanum chloride, praseodymium chloride, neodymium chloride, yttrium chloride, samarium trichloride are mixed to get to mixed liquor, the concentration of mixed liquor is controlled at 0.5mol/L, and hydro-oxidation sodium regulates material liquid pH value to be controlled at 3, stirs;
(2) add 1% the surfactant (sodium sulfonate) for mixed liquor of weight fraction, be placed in thermostat and leave standstill 1 hour after stirring, the temperature constant of thermostat is at 50 DEG C;
(3) under room temperature state, ammoniacal liquor is added in the feed liquid obtaining in step (2), control pH value 8, can obtain a kind of gelatinous precipitate;
(4) the gelatinous precipitate deionized water obtaining in step (3) is washed and dewatered;
(5) product dehydration in step (4) being obtained is put in kiln under 700 DEG C of conditions roasting 4 hours, and being then crushed to particle diameter is 5 microns, obtains described binary doped cerium zirconium carried catalyst.
The grain size of the carried catalyst that embodiment 3 prepares is: 2nm, the fresh specific area through 500-700 DEG C of calcining after 6 hours is: 171m
2/ g, 1000 DEG C calcining 10 hours after aging specific area be: 68m
2/ g, oxygen storage capacity is 1320umol/g.
Claims (10)
1. a binary doped cerium zirconium carried catalyst, is characterized in that: chemical composition composition and weight content are:
Cerium oxide 30-50 part, zirconia 30-50 part and other rare earth oxide 1-20 part;
Wherein, other rare earth oxide is: in lanthana, praseodymium oxide, neodymia, yittrium oxide or samarium oxide at least two kinds.
2. binary doped cerium zirconium carried catalyst according to claim 1, is characterized in that: chemical composition composition and weight content are:
Cerium oxide 30-50 part, zirconia 30-50 part, lanthana 0.5-1 part, praseodymium oxide 0.5-1 part, neodymia 2-3 part, yittrium oxide 3-4 part and samarium oxide 5-8 part.
3. a preparation method for the binary doped cerium zirconium carried catalyst described in claim 1 or 2, is characterized in that: comprise the following steps:
(1) aqueous solution of salt corresponding to cerium chloride, zirconium nitrate and other rare earth oxide is obtained to mixed liquor, the concentration of mixed liquor is controlled at 0.4-0.5mol/L, and material liquid pH value is controlled between 1-3, stirs;
(2) add the surfactant for the 0.1-1% of mixed liquor of weight fraction, after stirring, be placed on and in thermostat, leave standstill 1-2 hour;
(3) under room temperature state, ammoniacal liquor or NaOH are added in the feed liquid obtaining in step (2), control pH value between 8-10, can obtain a kind of gelatinous precipitate;
(4) the gelatinous precipitate deionized water obtaining in step (3) is washed and dewatered;
(5) product dehydration in step (4) being obtained is put in kiln roasting 4-6 hour under 500-700 DEG C of condition, after then pulverizing, obtains described binary doped cerium zirconium carried catalyst.
4. the preparation method of binary doped cerium zirconium carried catalyst according to claim 3, is characterized in that: the salt that in step (1), other rare earth oxide is corresponding is its corresponding chlorate or nitrate.
5. the preparation method of binary doped cerium zirconium carried catalyst according to claim 3, is characterized in that: the pH of step (1) feed liquid is by adding ammoniacal liquor, carbonic hydroammonium or NaOH adjustment.
6. the preparation method of binary doped cerium zirconium carried catalyst according to claim 3, is characterized in that: the surfactant described in step (2) is non-ionic surface active agent or anion surfactant.
7. the preparation method of binary doped cerium zirconium carried catalyst according to claim 6, is characterized in that: non-ionic surface active agent is one or more in polyethylene glycols, oleic acid or alkyl amine.
8. the preparation method of binary doped cerium zirconium carried catalyst according to claim 6, is characterized in that: anion surfactant is one or more in phosphate or sulfonate.
9. the preparation method of binary doped cerium zirconium carried catalyst according to claim 3, is characterized in that: in step (2), the temperature constant of thermostat is at 40-50 DEG C.
10. the preparation method of binary doped cerium zirconium carried catalyst according to claim 3, is characterized in that: the particle diameter after pulverizing in step (5) is 1-5 micron.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410395354.0A CN104128174B (en) | 2014-08-12 | 2014-08-12 | Binary doped cerium zirconium carried catalyst and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410395354.0A CN104128174B (en) | 2014-08-12 | 2014-08-12 | Binary doped cerium zirconium carried catalyst and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104128174A true CN104128174A (en) | 2014-11-05 |
| CN104128174B CN104128174B (en) | 2016-06-15 |
Family
ID=51801175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410395354.0A Active CN104128174B (en) | 2014-08-12 | 2014-08-12 | Binary doped cerium zirconium carried catalyst and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104128174B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107442117A (en) * | 2017-06-16 | 2017-12-08 | 福州大学 | A kind of exhaust gas catalytic conversion |
| CN108380198A (en) * | 2018-02-07 | 2018-08-10 | 广州德隆宝环保科技有限公司 | A kind of Zirconia composite nano-catalyst and preparation method thereof |
| CN109761259A (en) * | 2019-03-27 | 2019-05-17 | 淄博加华新材料资源有限公司 | A kind of high preparation method at colloidality cerium glue |
| CN109761260A (en) * | 2019-03-27 | 2019-05-17 | 淄博加华新材料资源有限公司 | Rare earth and the ceria and preparation method thereof of zirconium doping |
| CN110026179A (en) * | 2019-04-30 | 2019-07-19 | 山东国瓷功能材料股份有限公司 | A kind of cerium zirconium compound oxide and preparation method thereof of high oxygen storage capacity |
| CN114713218A (en) * | 2022-03-22 | 2022-07-08 | 西华师范大学 | Praseodymium-containing cerium-zirconium solid solution catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010036432A1 (en) * | 1994-12-06 | 2001-11-01 | Engelhard Corporation | Close coupled catalyst |
| CN101058443A (en) * | 2007-05-11 | 2007-10-24 | 华东理工大学 | Method for preparing Ce-Zr based nano rare earth composite oxide |
-
2014
- 2014-08-12 CN CN201410395354.0A patent/CN104128174B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010036432A1 (en) * | 1994-12-06 | 2001-11-01 | Engelhard Corporation | Close coupled catalyst |
| CN101058443A (en) * | 2007-05-11 | 2007-10-24 | 华东理工大学 | Method for preparing Ce-Zr based nano rare earth composite oxide |
Non-Patent Citations (1)
| Title |
|---|
| 刘蕾等: "高储氧能力的Ce-Zr-La-Y-Al储氧材料的制备", 《化学与生物工程》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107442117A (en) * | 2017-06-16 | 2017-12-08 | 福州大学 | A kind of exhaust gas catalytic conversion |
| CN108380198A (en) * | 2018-02-07 | 2018-08-10 | 广州德隆宝环保科技有限公司 | A kind of Zirconia composite nano-catalyst and preparation method thereof |
| CN109761259A (en) * | 2019-03-27 | 2019-05-17 | 淄博加华新材料资源有限公司 | A kind of high preparation method at colloidality cerium glue |
| CN109761260A (en) * | 2019-03-27 | 2019-05-17 | 淄博加华新材料资源有限公司 | Rare earth and the ceria and preparation method thereof of zirconium doping |
| CN109761259B (en) * | 2019-03-27 | 2021-04-02 | 淄博加华新材料有限公司 | Preparation method of cerium glue with high gelling property |
| CN109761260B (en) * | 2019-03-27 | 2021-10-12 | 淄博加华新材料有限公司 | Rare earth and zirconium doped cerium dioxide and preparation method thereof |
| CN110026179A (en) * | 2019-04-30 | 2019-07-19 | 山东国瓷功能材料股份有限公司 | A kind of cerium zirconium compound oxide and preparation method thereof of high oxygen storage capacity |
| CN110026179B (en) * | 2019-04-30 | 2021-11-19 | 山东国瓷功能材料股份有限公司 | Cerium-zirconium composite oxide with high oxygen storage capacity and preparation method thereof |
| CN114713218A (en) * | 2022-03-22 | 2022-07-08 | 西华师范大学 | Praseodymium-containing cerium-zirconium solid solution catalyst and preparation method and application thereof |
| CN114713218B (en) * | 2022-03-22 | 2023-08-22 | 西华师范大学 | Praseodymium-containing cerium-zirconium solid solution catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104128174B (en) | 2016-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104128174B (en) | Binary doped cerium zirconium carried catalyst and its preparation method | |
| CN104190438B (en) | High-performance cerium zirconium oxide and production method of high-performance cerium zirconium oxide | |
| CN104117363B (en) | Multi-element doping cerium zirconium carried catalyst and preparation method thereof | |
| CN101696034B (en) | Method for preparing nano-cerium oxide and zirconia solid solution | |
| CN107185547B (en) | C/Fe-FeVO4Composite photocatalyst and preparation method and application thereof | |
| CN106025178B (en) | It is a kind of to prepare the method for metal oxide and its application in lithium cell cathode material by template of MOF | |
| CN102259931A (en) | Method for preparing lithium manganese oxide battery material | |
| CN104528799B (en) | A kind of preparation method of magnesio rare earth hexa-aluminate superfine powder | |
| CN102698731B (en) | A kind of preparation method of high temperature resistant cerium zirconium solid solution | |
| CN104148116B (en) | The preparation method of low cost bigger serface cerium oxide | |
| CN101074490B (en) | Method for producing spherical, tie-shaped and octahedral polycrystalline Ce0.6Zr0.3Y0.1O2 particles of um sizes | |
| CN104128173B (en) | Low-cost and high-performance carried catalyst and preparation method thereof | |
| CN103936082B (en) | A kind of synthetic method of cobalt acid samarium nano-powder | |
| CN101891236B (en) | Method for synthesizing monodisperse samarium-doped rare earth cerium oxide nanocrystal | |
| CN104437458A (en) | Cerium-zirconium-based composite oxide catalytic material and preparation method thereof | |
| CN101830505A (en) | Scandium oxide-stabilizing zirconia powder and preparation method thereof | |
| CN102701246B (en) | A kind of preparation method of the rare earth modified aluminium oxide of high heat stability | |
| CN104148087B (en) | Praseodymium doped cerium zirconium carried catalyst and preparation method thereof | |
| CN109772290A (en) | A kind of preparation method of cerium zirconium sosoloid | |
| CN106732518A (en) | The preparation method of inexpensive bigger serface cerium-aluminium composite oxide | |
| CN101108340B (en) | Preparation method of zirconium manganese doped hexa- aluminate catalyzer | |
| CN102716735B (en) | Preparation method of ATP/ Ce-Ti sold soluble oxide composite material | |
| CN104028276B (en) | A kind of preparation method of compound molded breadth temperature methanation catalyst | |
| CN108573815B (en) | Preparation method of porous spherical NiO serving as electrode material of super capacitor | |
| CN102942204A (en) | Method for preparing cerium dioxide nanometer powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210126 Address after: 255400 west side of No.9 Jiahua Road, Jinshan Town, Linzi District, Zibo City, Shandong Province Patentee after: Zibo Jiahua New Material Co.,Ltd. Address before: 9 Jiahua Road, Jinshan Town, Linzi District, Zibo City, Shandong Province Patentee before: ZIBO ZAMR NEW MATERIAL RESOURCE Co.,Ltd. |
|
| TR01 | Transfer of patent right |