CN104128174B - Binary doped cerium zirconium carried catalyst and its preparation method - Google Patents
Binary doped cerium zirconium carried catalyst and its preparation method Download PDFInfo
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- CN104128174B CN104128174B CN201410395354.0A CN201410395354A CN104128174B CN 104128174 B CN104128174 B CN 104128174B CN 201410395354 A CN201410395354 A CN 201410395354A CN 104128174 B CN104128174 B CN 104128174B
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Abstract
The present invention relates to a kind of sosoloid carried catalyst, it is specifically related to a kind of binary doped cerium zirconium carried catalyst. Chemical composition forms and weight content is: cerium oxide 30-50 part, zirconium white 30-50 part, other rare-earth oxidation thing 1-20 part; Wherein, other rare-earth oxidation thing is: at least two kinds in lanthanum trioxide, Praseodymium trioxide, Neodymium trioxide, yttrium oxide or Samarium trioxide. The present invention also provides its preparation method, is mixed by all raw materials, adds tensio-active agent, obtains gelatinous precipitate, obtain product after roasting after then adjusting pH to 8-10. Instant invention overcomes the doping defect carrying out adulterating and producing in cerium zirconium carrier, greatly improve the performance index such as the thermostability of carried catalyst and aging specific surface area, oxygen storage capacity simultaneously; The present invention also provides its preparation method, and cost of material is cheap, and technological process is simple, is conducive to large-scale industrialization to produce.
Description
Technical field
The present invention relates to a kind of sosoloid carried catalyst, it is specifically related to a kind of binary doped cerium zirconium carried catalyst and its preparation method.
Background technology
Cerium oxide, as a kind of important support of the catalyst, has unique oxygen storage capacity and other excellent properties. Ce is there is in cerium ion under oxidation or reducing atmosphere3+And Ce4+Between redox reaction, thus realize storage oxygen and put oxygen function, contribute to realizing the catalyzed conversion of vehicle exhaust etc., but pure cerium oxide at high temperature very easily sinters, cause storing the decline of oxygen ability, form cerium zirconium base oxide sosoloid by the zirconium adulterating appropriate in cerium oxide, it is possible to improve cerium oxide high-temperature resistance to deterioration to a great extent and store oxygen performance, therefore, study on the synthesis round cerium zirconium base oxide sosoloid gets more and more people's extensive concerning. But there is the defects such as production cost height, powder reuniting is serious, specific surface area is little in existing cerium oxide carrying body catalyst.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of binary doped cerium zirconium carried catalyst, overcome the doping defect carrying out adulterating and producing in cerium zirconium carrier, greatly improve the performance index such as the thermostability of carried catalyst and aging specific surface area, oxygen storage capacity simultaneously; The present invention also provides its preparation method, and cost of material is cheap, and technological process is simple, is conducive to large-scale industrialization to produce.
Binary doped cerium zirconium carried catalyst of the present invention, chemical composition forms and weight content is:
Cerium oxide 30-50 part, zirconium white 30-50 part and other rare-earth oxidation thing 1-20 part;
Wherein, other rare-earth oxidation thing is: at least two kinds in lanthanum trioxide, Praseodymium trioxide, Neodymium trioxide, yttrium oxide or Samarium trioxide.
Preferred chemical composition forms and weight content is:
Cerium oxide 30-50 part, zirconium white 30-50 part, lanthanum trioxide 0.5-1 part, Praseodymium trioxide 0.5-1 part, Neodymium trioxide 2-3 part, yttrium oxide 3-4 part and Samarium trioxide 5-8 part.
Other rare-earth oxidation thing that adulterates in cerium zirconium carrier can improve its specific surface area and oxygen storage capacity, especially during samaria doped, the oxygen storage capacity of depositing of catalyzer has had very big improvement, when in carried catalyst during samaria doped, 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 becomes low on the contrary, cerium oxide 30-50 part, during zirconium white 30-50 part, Samarium trioxide preferably adds Samarium trioxide 5-8 part, within the scope of this carried catalyst deposit oxygen storage capacity and high-temperature stability the strongest. cerium zirconium carrier carries out adulterate and must overcome the generation of doping defect, because when introducing low price (or high price) cation oxide in cerium zirconium crystal, while positively charged ion occupies the crystallographic site of quadrivalent cerium ion, produce defect in order to the balance of retaining zone electric charge. and selective oxidation lanthanum 0.5-1 part of the present invention, Praseodymium trioxide 0.5-1 part, Neodymium trioxide 2-3 part, yttrium oxide 3-4 part and Samarium trioxide 5-8 part are added in cerium oxide 30-50 part and zirconium white 30-50 part jointly, overcome the generation of doping defect significantly.
The preparation method of described binary doped cerium zirconium carried catalyst, comprises the following steps:
(1) aqueous solution by salt corresponding to Cerium II Chloride, zirconium nitrate and other rare-earth oxidation thing obtains mixed solution, and the concentration of mixed solution controls at 0.4-0.5mol/L, and material liquid pH value controls between 1 and 3, stirs;
(2) add the tensio-active agent of the 0.1-1% for mixed solution of weight fraction, stir and be placed in thermostatic bath to leave standstill 1-2 hour after evenly;
(3) ammoniacal liquor or sodium hydroxide being added in step (2) in the feed liquid obtained under room temperature state, control ph, between 8-10, can obtain a kind of gelatinous precipitate;
(4) undertaken washing by the gelatinous precipitate deionized water obtained in step (3) and dewater;
(5) it is put in kiln under 500-700 DEG C of condition by the product that dehydration in step (4) obtains roasting 4-6 hour, after then pulverizing, obtains described binary doped cerium zirconium carried catalyst.
Wherein:
The salt that in step (1), other rare-earth oxidation thing is corresponding is chlorate or the nitrate of its correspondence.
The pH of step (1) feed liquid is by adding ammoniacal liquor, bicarbonate of ammonia or sodium hydroxide adjustment.
Tensio-active agent described in step (2) is nonionogenic tenside or anion surfactant.
Nonionogenic tenside is one or more in polyethylene glycols, oleic acid or alkyl amine.
Anion surfactant is one or more in phosphoric acid salt or sulfonate.
In step (2), the homo(io)thermism of thermostatic bath 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, the doping defect carrying out adulterating and producing in cerium zirconium carrier is overcome.
(2) the present invention improves the performance index such as thermostability and aging specific surface area, oxygen storage capacity of carried catalyst greatly, the carried catalyst prepared exists with sosoloid form, its grain fineness number is: 1-10nm, and the fresh specific surface area after calcining 4-6 hour through 500-700 DEG C is: 150-180m2/ g, 1000 DEG C calcining 10 hours after aging specific surface area be: 50-80m2/ g, oxygen storage capacity is higher than 1000umol/g.
(3) cost of material is cheap, and technological process is simple, is conducive to large-scale industrialization to produce.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
A kind of unit of preparation doped with cerium zirconium carried catalyst, chemical composition forms and weight content is:
Cerium oxide 30 parts, zirconium white 30 parts, lanthanum trioxide 0.5 part, Praseodymium trioxide 0.5 part, Neodymium trioxide 2 parts, yttrium oxide 3 parts and Samarium trioxide 5 parts.
Preparation method comprises the following steps:
(1) Cerium II Chloride, zirconium nitrate, Lanthanum trichloride, praseodymium chloride, Neodymium trichloride, Yttrium trichloride, samarium trichloride being mixed to get mixed solution, the concentration of mixed solution controls at 0.45mol/L, adds ammoniacal liquor and regulates material liquid pH value to control to stir 2;
(2) what add weight fraction is the tensio-active agent (polyoxyethylene glycol) of the 0.5% of mixed solution, stirs and is placed in thermostatic bath to leave standstill 1.5 hours after evenly, and the homo(io)thermism of thermostatic bath is at 45 DEG C;
(3) being added by ammoniacal liquor in step (2) under room temperature state in the feed liquid obtained, control ph, 9, can obtain a kind of gelatinous precipitate;
(4) undertaken washing by the gelatinous precipitate deionized water obtained in step (3) and dewater;
(5) being put in kiln under 600 DEG C of conditions by the product that dehydration in step (4) obtains roasting 5 hours, being then crushed to particle diameter is 3 microns, obtains described binary doped cerium zirconium carried catalyst.
The grain fineness number of the carried catalyst that embodiment 1 prepares is: 5nm, and the fresh specific surface area after calcining 6 hours through 500-700 DEG C is: 180m2/ g, 1000 DEG C calcining 10 hours after aging specific surface area be: 80m2/ g, oxygen storage capacity is 1660umol/g.
Embodiment 2
Preparing a kind of binary doped cerium zirconium carried catalyst, chemical composition forms and weight content is:
Cerium oxide 50 parts, zirconium white 50 parts, lanthanum trioxide 1 part, Praseodymium trioxide 0.7 part, Neodymium trioxide 2.5 parts, yttrium oxide 3.5 parts and Samarium trioxide 7 parts.
Preparation method comprises the following steps:
(1) Cerium II Chloride, zirconium nitrate, Lanthanum trichloride, praseodymium chloride, Neodymium trichloride, Yttrium trichloride, samarium trichloride being mixed to get mixed solution, the concentration of mixed solution controls at 0.4mol/L, adds bicarbonate of ammonia and regulates material liquid pH value to control to stir 1;
(2) what add weight fraction is the tensio-active agent (oleic acid) of the 0.1% of mixed solution, stirs and is placed in thermostatic bath to leave standstill 2 hours after evenly, and the homo(io)thermism of thermostatic bath is at 40 DEG C;
(3) being added by sodium hydroxide in step (2) under room temperature state in the feed liquid obtained, control ph, 10, can obtain a kind of gelatinous precipitate;
(4) undertaken washing by the gelatinous precipitate deionized water obtained in step (3) and dewater;
(5) being put in kiln under 500 DEG C of conditions by the product that dehydration in step (4) obtains roasting 6 hours, being then crushed to particle diameter is 1 micron, obtains described binary doped cerium zirconium carried catalyst.
The grain fineness number of the carried catalyst that embodiment 2 prepares is: 8nm, and the fresh specific surface area after calcining 6 hours through 500-700 DEG C is: 160m2/ g, 1000 DEG C calcining 10 hours after aging specific surface area be: 75m2/ g, oxygen storage capacity is 1400umol/g.
Embodiment 3
Preparing a kind of binary doped cerium zirconium carried catalyst, chemical composition forms and weight content is:
Cerium oxide 40 parts, zirconium white 45 parts, lanthanum trioxide 0.8 part, Praseodymium trioxide 1 part, Neodymium trioxide 3 parts, yttrium oxide 4 parts and Samarium trioxide 8 parts.
Preparation method comprises the following steps:
(1) Cerium II Chloride, zirconium nitrate, Lanthanum trichloride, praseodymium chloride, Neodymium trichloride, Yttrium trichloride, samarium trichloride being mixed to get mixed solution, the concentration of mixed solution controls at 0.5mol/L, and hydro-oxidation sodium regulates material liquid pH value to control to stir 3;
(2) what add weight fraction is the tensio-active agent (sodium sulfonate) of the 1% of mixed solution, stirs and is placed in thermostatic bath to leave standstill 1 hour after evenly, and the homo(io)thermism of thermostatic bath is at 50 DEG C;
(3) being added by ammoniacal liquor in step (2) under room temperature state in the feed liquid obtained, control ph, 8, can obtain a kind of gelatinous precipitate;
(4) undertaken washing by the gelatinous precipitate deionized water obtained in step (3) and dewater;
(5) being put in kiln under 700 DEG C of conditions by the product that dehydration in step (4) obtains roasting 4 hours, being then crushed to particle diameter is 5 microns, obtains described binary doped cerium zirconium carried catalyst.
The grain fineness number of the carried catalyst that embodiment 3 prepares is: 2nm, and the fresh specific surface area after calcining 6 hours through 500-700 DEG C is: 171m2/ g, 1000 DEG C calcining 10 hours after aging specific surface area be: 68m2/ g, oxygen storage capacity is 1320umol/g.
Claims (9)
1. a binary doped cerium zirconium carried catalyst, it is characterised in that: chemical composition forms and weight content is:
Cerium oxide 30-50 part, zirconium white 30-50 part, lanthanum trioxide 0.5-1 part, Praseodymium trioxide 0.5-1 part, Neodymium trioxide 2-3 part, yttrium oxide 3-4 part and Samarium trioxide 5-8 part.
2. the preparation method of a binary doped cerium zirconium carried catalyst according to claim 1, it is characterised in that: comprise the following steps:
(1) aqueous solution by salt corresponding to Cerium II Chloride, zirconium nitrate and other rare-earth oxidation thing obtains mixed solution, and the concentration of mixed solution controls at 0.4-0.5mol/L, and material liquid pH value controls between 1 and 3, stirs;
(2) add the tensio-active agent that weight fraction is the 0.1-1% of mixed solution, stir and be placed in thermostatic bath to leave standstill 1-2 hour after evenly;
(3) ammoniacal liquor or sodium hydroxide being added in step (2) in the feed liquid obtained under room temperature state, control ph, between 8-10, can obtain a kind of gelatinous precipitate;
(4) undertaken washing by the gelatinous precipitate deionized water obtained in step (3) and dewater;
(5) it is put in kiln under 500-700 DEG C of condition by the product that dehydration in step (4) obtains roasting 4-6 hour, after then pulverizing, obtains described binary doped cerium zirconium carried catalyst.
3. the preparation method of binary doped cerium zirconium carried catalyst according to claim 2, it is characterised in that: the salt that in step (1), other rare-earth oxidation thing is corresponding is chlorate or the nitrate of its correspondence.
4. the preparation method of binary doped cerium zirconium carried catalyst according to claim 2, it is characterised in that: the pH of step (1) feed liquid is by adding ammoniacal liquor, bicarbonate of ammonia or sodium hydroxide adjustment.
5. the preparation method of binary doped cerium zirconium carried catalyst according to claim 2, it is characterised in that: the tensio-active agent described in step (2) is nonionogenic tenside or anion surfactant.
6. the preparation method of binary doped cerium zirconium carried catalyst according to claim 5, it is characterised in that: nonionogenic tenside is one or more in polyethylene glycols, oleic acid or alkyl amine.
7. the preparation method of binary doped cerium zirconium carried catalyst according to claim 5, it is characterised in that: anion surfactant is one or more in phosphoric acid salt or sulfonate.
8. the preparation method of binary doped cerium zirconium carried catalyst according to claim 2, it is characterised in that: in step (2), the homo(io)thermism of thermostatic bath is at 40-50 DEG C.
9. the preparation method of binary doped cerium zirconium carried catalyst according to claim 2, it is characterised in that: the particle diameter after pulverizing in step (5) is 1-5 micron.
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| CN107442117B (en) * | 2017-06-16 | 2019-07-09 | 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 |
| 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 |
| 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 |
| 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 |
| 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 |
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| 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 |
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| 高储氧能力的Ce-Zr-La-Y-Al储氧材料的制备;刘蕾等;《化学与生物工程》;20121231;第29卷(第3期);第43-47页 * |
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