CN1470455A - Composite cerium-zirconium-barium oxides and preparing method thereof - Google Patents
Composite cerium-zirconium-barium oxides and preparing method thereof Download PDFInfo
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- CN1470455A CN1470455A CNA021362734A CN02136273A CN1470455A CN 1470455 A CN1470455 A CN 1470455A CN A021362734 A CNA021362734 A CN A021362734A CN 02136273 A CN02136273 A CN 02136273A CN 1470455 A CN1470455 A CN 1470455A
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- CN
- China
- Prior art keywords
- zirconium
- cerium
- barium
- nitrate
- barium oxides
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Links
- 239000002131 composite material Substances 0.000 title claims description 22
- HIPAVDUQVNMVSJ-UHFFFAOYSA-N [O-2].[Ba+2].[Zr+4].[Ce+3] Chemical class [O-2].[Ba+2].[Zr+4].[Ce+3] HIPAVDUQVNMVSJ-UHFFFAOYSA-N 0.000 title claims description 20
- 238000000034 method Methods 0.000 title claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 14
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052788 barium Inorganic materials 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001960 metal nitrate Inorganic materials 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- UXTQXSXAJLBMOC-UHFFFAOYSA-N [Ce].[Zr].[Ba] Chemical compound [Ce].[Zr].[Ba] UXTQXSXAJLBMOC-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000002360 preparation method Methods 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- -1 polyoxyethylene Polymers 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- 229910001864 baryta Inorganic materials 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 230000029087 digestion Effects 0.000 claims 1
- 239000002243 precursor Substances 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 238000004821 distillation Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 229920000151 polyglycol Polymers 0.000 abstract 1
- 239000010695 polyglycol Substances 0.000 abstract 1
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a kind of super tiny cerium-zirconium-barium compound oxide and the manufacturing method. The molecular formula is CexZr1-xBayOz, the mol proportion of cerium, zirconium and barium is: Ce=X(X=0.1-1) : Xr=1-X: Ba=Y(Y=0.1-0.5), it uses metal nitrate such as cerium nitrate, zirconium nitrate, barium nitrate as materials, through polyglycol high molecular surface decorating agent, uses butyl alcohol azeotropy distillation. The baked temperature is 600 deg.C -700 deg.C, the time is 3-4 hours.
Description
Technical field
The present invention relates to a kind of cerium zirconium compound oxide and preparation method thereof, particularly ultra-fine composite cerium-zirconium-barium oxides and preparation method thereof.
Background technology
Because cerium zirconium compound oxide has unique catalytic performance and stores the oxygen performance, can be used for the coating material of vehicle tail gas triple effect catalyzer (three way catalyst) carrier, also can be used as oxidation catalyst carrier and active ingredient.Ultra-fine cerium zirconium compound oxide nano material except that chemical purposes, has important use in high strength ceramic material synthetic.Existing cerium zirconium compound oxide is a two-pack, and its method for preparing cerium zirconium compound oxide is based on traditional sol-gel method, and this method is to make by the method that adds citric acid complexing agent.This technology exists specific surface big inadequately, phenomenons such as the easy reunion of particle, and particularly it is used for the vehicle tail gas triple effect catalyzer owing to thermostability is subjected to certain limitation inadequately well.Also have and adopt the Azotropic distillation method preparation, but prepared be single component oxide compound (reference J-TJiu, Yue Ge, S-RZhang, L-PLi, Fan Tu, H-SZhu, J.of Inorg.Mater.16 (5) 2001, and 867), not about the composite cerium-zirconium-barium oxides preparation method.
Summary of the invention
The composite cerium-zirconium-barium oxides and preparation method thereof that the purpose of this invention is to provide a kind of ultrafine particle of high-ratio surface.
Composite cerium-zirconium-barium oxides provided by the invention, molecular formula are Ce
xZr
1-xB
yO
z, the molar ratio of described component cerium, zirconium, barium is Ce=X (X=0.1～1): Zr=1-X: Ba=Y (Y=0.1～0.5), cerium: zirconium: the optimum proportion of barium is 0.7: 0.3: 0.1 (mol ratio).
The preparation method of composite cerium-zirconium-barium oxides provided by the invention is achieved in that with the metal nitrate to be raw material, by polyoxyethylene glycol (molecular weight 20000) macromolecular surface modification agent, the method that adopts organic solvent propyl carbinol and the formed azeotrope of water thoroughly to deviate from presoma moisture content makes.Metal nitrate refers to cerous nitrate, zirconium nitrate, nitrate of baryta.Maturing temperature is 600～700 ℃, and roasting time is 3～4 hours.Its preparation process is: (1) is by above-mentioned cerium X (X=0.1～1): zirconium 1-X: barium Y (Y=0.1～0.5) molar ratio calculates and takes by weighing respective amount cerous nitrate, zirconium nitrate, nitrate of baryta, adds the suitable quantity of water dissolving, and is stand-by.(2) in the aqueous solution that contains polyoxyethylene glycol (molecular weight 20000), slowly drip 1. described mixing solutions, under the magnetic agitation condition, be adjusted to certain pH value with ammoniacal liquor after, solution is kept the regular hour under the certain temperature condition, make gel.(3) get the gel suction filtration except that desolvating, repeatedly after the detergent gel it is dissolved in the propyl carbinol, stir with distilled water, heating, azeotrope is steamed, treat that moisture content removes fully after, temperature is raised to the boiling point of propyl carbinol, continue the backflow certain hour with this understanding, stop heating, the evaporate to dryness propyl carbinol gets faint yellow powder then, with this powder roasting 3～4h under 600 ℃～700 ℃ conditions, make the composite cerium-zirconium-barium oxides powder.
Preparation technology of the present invention is simple, and the composite cerium-zirconium-barium oxides diameter of particle that makes reaches nano level, specific surface height, better heat stability.
Embodiment
Embodiment 1: the preparation of composite cerium-zirconium-barium oxides powder, the steps include: that (1) is Ce=X (X is 0.1～1) in the ratio of Ce: Zr: Ba, and Zr=1-X, the mol ratio of Ba=Y (Y=0.1～0.5) is calculated the Ce (NO that takes by weighing respective amount
3)
36H
2O, Zr (NO
3)
45H
2O, Ba (NO
3)
2, add the suitable quantity of water dissolving, stand-by.(2) contain at 400ml and slowly drip 1. described mixing solutions in the aqueous solution of polyoxyethylene glycol (molecular weight 20000) 20g, under the magnetic agitation condition,, solution is remained under-5 ℃ of conditions and kept 24 hours greater than after 9 with the pH value of ammoniacal liquor regulator solution, make gel.(3) get the gel suction filtration and remove and to desolvate, repeatedly it is dissolved in after the detergent gel with distilled water in 10 times the propyl carbinol, stir, heat in three-necked bottle, when reaching 97 ℃, azeotrope is steamed, after treating that moisture content removes fully, temperature is raised to 118 ℃ of the boiling points of propyl carbinol rapidly, continues backflow 0.5h with this understanding, stop heating, the evaporate to dryness propyl carbinol gets faint yellow powder, with this powder roasting 3～4h under 600～700 ℃ of conditions then,, make Ce
xZr
1-xBa
yO
2Composite oxide powder.
Embodiment 2:
Ratio in Ce: Zr: Ba is Ce=0.7, Zr=0.3, and the mol ratio of Ba=0.1 is calculated and is taken by weighing 12.159gCe (NO
3)
36H
2O, 5.152gZr (NO
3)
45H
2O, 1.048gBa (NO
3)
2, add the suitable quantity of water dissolving, stand-by.Following steps are identical with embodiment 1.
The Ce that present embodiment makes
0.7Zr
0.3Ba
0.1O
2.1Composite oxide powder, particle diameter reach nano level (10～20nm), specific surface (118.96m
2/ g), after 1000 ℃ of pyroprocessing, composite cerium-zirconium-barium oxides does not have reunites and the particle growth phenomenon.
Claims (8)
1. composite cerium-zirconium-barium oxides, molecular formula is Ce
xZr
1-xBa
yO
z, the molar ratio that it is characterized in that described cerium, zirconium, barium is Ce=X (X=0.1～1): Zr=1-X: Ba=Y (Y=0.1～0.5).
2. according to the described composite cerium-zirconium-barium oxides of claim 1, the ratio that it is characterized in that described cerium, zirconium, barium is 0.7: 0.3: 0.1 (mol ratio).
3. the preparation method of the described composite cerium-zirconium-barium oxides of claim 1, it is characterized in that with metal nitrate cerous nitrate, zirconium nitrate, nitrate of baryta be raw material, by polyoxyethylene glycol (molecular weight 20000) macromolecular surface modification agent, the method that adopts organic solvent propyl carbinol and the formed azeotrope of water thoroughly to deviate from presoma moisture makes, maturing temperature is 600 ℃～700 ℃, and roasting time is 3～4 hours.
4. the preparation method of composite cerium-zirconium-barium oxides according to claim 3 the steps include:
(1) by cerium: zirconium: barium molar ratio Ce=X (X=0.1～1): cerous nitrate, zirconium nitrate, nitrate of baryta that Zr=1-X: Ba=Y (Y=0.1～0.5) calculated and took by weighing respective amount add the suitable quantity of water dissolving, and be stand-by.
(2) in the aqueous solution that contains polyoxyethylene glycol (molecular weight 20000), slowly drip 1. described mixing solutions, under the magnetic agitation condition, be adjusted to certain pH value with ammoniacal liquor after, solution is kept the regular hour under the certain temperature condition, make gel.
(3) get the gel suction filtration except that desolvating, repeatedly after the detergent gel it is dissolved in the propyl carbinol, stir with distilled water, heating, azeotrope is steamed, treat that moisture content removes fully after, temperature is raised to the boiling point of propyl carbinol, continue backflow 0.5h with this understanding, stop heating, the evaporate to dryness propyl carbinol gets faint yellow powder then, with this powder roasting 3～4h under 600～700 ℃ of conditions, make composite cerium-zirconium-barium oxides.
5. the preparation method of composite cerium-zirconium-barium oxides according to claim 4, the described propyl carbinol solvent load of its feature is 10 times of cerium zirconium barium precursor xerogel weight.
6. the preparation method of composite cerium-zirconium-barium oxides according to claim 4, the described pH value of solution value of regulating with ammoniacal liquor of its feature is greater than 9.
7. the preparation method of composite cerium-zirconium-barium oxides according to claim 4, the cooling temperature of the described gel of its feature is-5 ℃, digestion time is 24 hours.
8. composite cerium-zirconium-barium oxides preparation method according to claim 4, described metal-salt of its feature and polyoxyethylene glycol (molecular weight 20000) temperature of reaction is a normal temperature, reaction pressure is a normal pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021362734A CN1179879C (en) | 2002-07-25 | 2002-07-25 | Composite cerium-zirconium-barium oxides and preparing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021362734A CN1179879C (en) | 2002-07-25 | 2002-07-25 | Composite cerium-zirconium-barium oxides and preparing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1470455A true CN1470455A (en) | 2004-01-28 |
| CN1179879C CN1179879C (en) | 2004-12-15 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224394A (en) * | 2013-04-19 | 2013-07-31 | 天津大学 | Lithium carbonate modified cerium barium zirconate proton conductor material and preparation method thereof |
| CN106745169A (en) * | 2016-12-09 | 2017-05-31 | 上海应用技术大学 | A kind of bigger serface mesoporous cerium oxide zirconium solid solution and preparation method thereof |
| CN107583638A (en) * | 2017-11-01 | 2018-01-16 | 辽宁大学 | A kind of double frequency sound catalyst and its preparation method and application |
-
2002
- 2002-07-25 CN CNB021362734A patent/CN1179879C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224394A (en) * | 2013-04-19 | 2013-07-31 | 天津大学 | Lithium carbonate modified cerium barium zirconate proton conductor material and preparation method thereof |
| CN106745169A (en) * | 2016-12-09 | 2017-05-31 | 上海应用技术大学 | A kind of bigger serface mesoporous cerium oxide zirconium solid solution and preparation method thereof |
| CN107583638A (en) * | 2017-11-01 | 2018-01-16 | 辽宁大学 | A kind of double frequency sound catalyst and its preparation method and application |
| CN107583638B (en) * | 2017-11-01 | 2019-12-06 | 辽宁大学 | double-frequency acoustic catalyst and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1179879C (en) | 2004-12-15 |
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