CN100376484C - Preparation method of nano cerium zirconium compound oxide and its application - Google Patents
Preparation method of nano cerium zirconium compound oxide and its application Download PDFInfo
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- CN100376484C CN100376484C CNB2003101229946A CN200310122994A CN100376484C CN 100376484 C CN100376484 C CN 100376484C CN B2003101229946 A CNB2003101229946 A CN B2003101229946A CN 200310122994 A CN200310122994 A CN 200310122994A CN 100376484 C CN100376484 C CN 100376484C
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- cerium
- hydrazine
- cerium zirconium
- zirconium
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Abstract
The present invention discloses a nanometer cerium zirconium composite oxide and a preparation method thereof. The nanometer cerium zirconium composite oxide is particularly obtained by the method that formic acid and hydrazine are added in lead compounds of cerium and zirconium, and then, an obtained mixture is decomposed at high temperature under the atmosphere of air. The dosage of the hydrazine or hydrazine nitrate is greatly reduced, and thus, cost is reduced. The cerium zirconium composite oxide prepared by the present invention contains 5 to 99% (weight percentage) of CeO2 and 0 to 94% (weight percentage) of ZrO2, wherein crystal grain particle diameters of the CeO2 and the ZrO2 are smaller than or equal to 100 nm, and the loss on ignition fired for one hour at 900 DEG C is smaller than or equal to 5%. The nanometer cerium zirconium composite oxide can be used for grinding materials, catalysts, energy saving materials, etc.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of preparation method and application of nanometer cerium zirconium oxide.
Background technology
Cerium oxide and cerium zirconium compound oxide can be used as abrasive substance, and the interpolation material of (improveing its some physicals) in rubber and the high polymer product increases the catalyzer of combustion heat energy in the catalytic field, and handle the catalyzer from the oil engine combustion gas.France Luo Na Blanc Co., Ltd (patent No. is 94194552.9 and 96196505.3), Japanese Santoku Metal Industry Co., Ltd (patent No. is 95119160.8 and 95119164.0), Nippon Shokubai Kagaku Kogyo Co., Ltd's (patent No. is 89103518.4) and Yaolong Non-ferrous Metal Co. Ltd., Shanghai have all obtained relevant patent with Tongji University's (patent No. is 99102251.3).
The preparation method of cerium, zirconium mixed oxide is a thermal decomposition method in the market, and its process can be expressed as:
The mixture of heat decomposable cerium, zirconium compounds (being lead compound) in air, heat cerium zirconium compound oxide.
Preparation method according to lead compound can be divided into two classes again.
1, wet method (coprecipitation method): three moral metals and catalyst chemical industry Co., Ltd. as French Luo Na Blanc Co., Ltd and Japan all belong to this type of.Its operation steps is: the acidic solution that will contain certain proportion cerium, zirconium ion is poured in the precipitant solution (as ammonia soln), and precipitation after filtration, after the washing, drying, obtain lead compound.
This method flow process is longer, and the cerium zirconium compound oxide granularity of preparing is big, specific surface area is less.
2, dry method: Yaolong Non-ferrous Metal Co. Ltd., Shanghai and patent that Tongji University holds just belong to this type of, this technology is with heat decomposable cerium, zirconium compounds (as muriate, nitrate, carbonate, oxalate, oxyhydroxide) mechanically mixing according to a certain percentage, adds liquid hydrazine or hydrazine compound (hydrazine nitrate) then and constitutes precursor.
This method technology is simple, owing in thermal decomposition process, produce a large amount of gases and heat as the hydrazine or the hydrazine compound of additive, thereby can make the nanometer cerium zirconium oxide that particle is thin, specific surface area big, activity is high.
The shortcoming of this method has two.The first: adopt basic zirconium chloride as the zirconium source in the lead compound, inevitably cause the Cl that contains in the product nanometer cerium zirconium oxide about 1%
-, and Cl
-Should avoid as far as possible.Next is: as the hydrazine or the hydrazine nitrate large usage quantity of additive, cost is higher
Summary of the invention
The object of the present invention is to provide a kind of Cl that do not contain
-, and the preparation method of the nanometer cerium zirconium oxide that greatly reduces of hydrazine or hydrazine nitrate consumption (being cost).
The preparation method of the nanometer cerium zirconium oxide that the present invention proposes, but by adding formic acid and hydrazine in the lead compound of forming by the heat-decomposing compound of cerium and zirconium, thermolysis under 350-800 ℃ of temperature in air atmosphere then can obtain nanometer cerium zirconium oxide.
As everyone knows, formic acid only contains a C atom, and its structural formula is
Its metal-salt very easily decomposes, in this preparation method, formic acid is added lead compound, make cerium and zirconium part or major part exist with the form of formate, and with fines (even with molecule, ion concentration) mixing mutually, so not only can obviously reduce the consumption of another additive hydrazine, and can guarantee that thermal decomposition product (being cerium zirconium compound oxide) particle is thin, specific surface area is big, phase composite is single, we can say that selecting formic acid and hydrazine to form composite additive is of the present invention one big characteristics.
Among the above-mentioned preparation method, the add-on of additive is that say by making the 100g cerium zirconium compound oxide: the formic acid consumption is no more than 70ml, is generally 20-70ml; The hydrazine consumption is no more than 50ml, is generally 10-50ml.
The CeO that contains 5-99% weight in the cerium zirconium compound oxide that the present invention prepares
2ZrO with 0-94% weight
2, its size of microcrystal≤100nm, these composite oxides are through 1 hour igloss amount≤5% of 900 ℃ of calcinations.Still kept single-phase in 12 hours through 1000 ℃ of calcinations.
Above-mentioned composite oxides also contain other element of 0.01-10% weight.These elements comprise silicon, aluminium, molybdenum, hafnium and rare earth element.
The specific surface area of above-mentioned composite oxides is 5-120m
2/ g.
Among the above-mentioned preparation method, described lead compound can adopt nitrate, carbonate, oxyhydroxide or its mixture of cerium, zirconium.
Not only particle is thin, specific surface area big for this nanometer cerium zirconium oxide of the present invention's preparation, activity is high, phase composite is single but also thermostability might as well.In addition, do not contain Cl in the composite oxides
-, the consumption of hydrazine or hydrazine nitrate significantly reduces, and cost reduces.
Above-mentioned nanometer cerium zirconium oxide can be used as abrasive substance; Useful as catalysts is as the catalyst aid in the automobile exhaust purifier: also can be used as the property-modifying additive in macromolecular material (as rubber, the nylon) goods.
The application of nanometer cerium zirconium oxide can be used as the energy-saving material that increases the combustion gas heating efficiency.
Embodiment
The present invention is further described by the following embodiment.
Embodiment 1, gets to prepare 20g CeO
2Cerous hydroxide, add 5ml formic acid (concentration 85%) and mix thoroughly, add 2ml hydrazine hydrate (concentration 80%) again, mix thoroughly, put into 100 ℃ of oven dry of baking oven.Dry thing is put into the magnetic crucible, place in the retort furnace, progressively be warming up to 500 ℃, and kept 0.5 hour, can obtain nano-cerium oxide, specific surface area is 80m
2/ g, crystal grain are 15-25nm.
Embodiment 2, take by weighing respectively to make 20g cerium zirconium compound oxide (Ce
0.75Zr
0.25O
2) cerous carbonate and zirconium carbonate, cerous carbonate and 14ml formic acid (concentration 85%) are mixed thoroughly, add zirconium carbonate then, mix thoroughly, add 10ml hydrazine hydrate (concentration 80%) at last, mix thoroughly again, put into 100 ℃ of oven dry of baking oven.Dry thing is put into the magnetic crucible, place in the retort furnace, progressively be warming up to 400 ℃, and kept 0.5 hour, can obtain nanometer cerium zirconium oxide (Ce
0.75Zr
0.25O
2), specific surface area is 40m
2/ g, crystal grain are 50-60nm.
Embodiment 3, take by weighing to make 20g cerium zirconium compound oxide (Ce
0.4Zr
0.6O
2) cerous carbonate and zirconium carbonate, mix thoroughly, add 10ml formic acid (concentration 85%), mix thoroughly, add 8ml hydrazine hydrate (concentration 80%) again, mix thoroughly, put into 100 ℃ of oven dry of baking oven.Dry thing is put into the magnetic crucible, place in the retort furnace, progressively be warming up to 600 ℃, kept 0.5 hour, can obtain nanometer cerium zirconium oxide (Ce
0.4Zr
0.6O
2), specific surface area is 34m
2/ g, crystal grain are 80-90nm.
Claims (1)
1. the preparation method of a nanometer cerium zirconium oxide is characterized in that adding formic acid and hydrazine in the lead compound of cerium and zirconium, and by making 100g cerium zirconium composite oxide compound, the addition of formic acid is 20-70ml, and the addition of hydrazine is 10-50ml; Thermolysis and make nanometer cerium zirconium oxide under 350-800 ℃ of temperature in air atmosphere then; Wherein, one or more in the nitrate of the lead compound of described cerium and zirconium employing cerium and zirconium, carbonate, the oxyhydroxide.
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|---|---|---|---|
| CNB2003101229946A CN100376484C (en) | 2003-12-30 | 2003-12-30 | Preparation method of nano cerium zirconium compound oxide and its application |
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|---|---|---|---|
| CNB2003101229946A CN100376484C (en) | 2003-12-30 | 2003-12-30 | Preparation method of nano cerium zirconium compound oxide and its application |
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| CN1556042A CN1556042A (en) | 2004-12-22 |
| CN100376484C true CN100376484C (en) | 2008-03-26 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1764346A1 (en) * | 2005-09-16 | 2007-03-21 | Omya Development AG | Process of preparing mineral material with particular ceria-containing zirconium oxide grinding beads, obtained products and their uses |
| CN100417599C (en) * | 2006-10-23 | 2008-09-10 | 浙江理工大学 | Method for preparing tetragonal phase zirconium oxide nano powder |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1137784A (en) * | 1993-12-24 | 1996-12-11 | 罗纳·布朗克化学公司 | Composition precursor and cerium and zirconium mixed oxide based composition, method for its preparation and use thereof |
| CN1255105A (en) * | 1997-04-04 | 2000-05-31 | 罗狄亚稀土公司 | Cerium oxides, zirconium oxides, Ce/Zr mixed oxides and Ce/Zr solid solutions having improved thermal stability and oxygen storage capacity |
| CN1263868A (en) * | 1999-02-15 | 2000-08-23 | 上海跃龙有色金属有限公司 | Nm-class compound Ce-Zr oxide and its preparing process and application |
| CN1369460A (en) * | 2002-03-18 | 2002-09-18 | 内蒙古工业大学 | Process for preparing Ce-Zr based composite oxide |
| CN1403376A (en) * | 2002-10-15 | 2003-03-19 | 清华大学 | Cerium-base quaternary nano level composite RE oxide and its prepn process |
-
2003
- 2003-12-30 CN CNB2003101229946A patent/CN100376484C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1137784A (en) * | 1993-12-24 | 1996-12-11 | 罗纳·布朗克化学公司 | Composition precursor and cerium and zirconium mixed oxide based composition, method for its preparation and use thereof |
| CN1255105A (en) * | 1997-04-04 | 2000-05-31 | 罗狄亚稀土公司 | Cerium oxides, zirconium oxides, Ce/Zr mixed oxides and Ce/Zr solid solutions having improved thermal stability and oxygen storage capacity |
| CN1263868A (en) * | 1999-02-15 | 2000-08-23 | 上海跃龙有色金属有限公司 | Nm-class compound Ce-Zr oxide and its preparing process and application |
| CN1369460A (en) * | 2002-03-18 | 2002-09-18 | 内蒙古工业大学 | Process for preparing Ce-Zr based composite oxide |
| CN1403376A (en) * | 2002-10-15 | 2003-03-19 | 清华大学 | Cerium-base quaternary nano level composite RE oxide and its prepn process |
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