CN100334001C - Medium-low temperature solid-solid reaction method for preparing nano grade cerium-zirconium composite oxide solid solution - Google Patents
Medium-low temperature solid-solid reaction method for preparing nano grade cerium-zirconium composite oxide solid solution Download PDFInfo
- Publication number
- CN100334001C CN100334001C CNB2004100514340A CN200410051434A CN100334001C CN 100334001 C CN100334001 C CN 100334001C CN B2004100514340 A CNB2004100514340 A CN B2004100514340A CN 200410051434 A CN200410051434 A CN 200410051434A CN 100334001 C CN100334001 C CN 100334001C
- Authority
- CN
- China
- Prior art keywords
- solid
- low temperature
- zirconium
- nano
- carbonate
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention discloses a method for preparing a solid solution of cerium zirconium composite oxides of a nanometer stage by a medium and low temperature solid-solid reaction method, which is a preparation method of a composite oxide solid solution of the nanometer stage based on cerium oxide and zirconium oxide, wherein the composite oxide solid solution comprises the cerium oxide and the zirconium oxide. The cerium carbonate and the zirconium carbonate are used as a raw material by the method of the present invention, and oxalic acid is added in the cerium carbonate and the zirconium in proportion. Then, through ball milling and calcination, the composite oxide solid solution is prepared. The crystallization degree of the composite oxide solid solution is high, crystal forms are regular cubic systems, granularity is 20 to 70 nm and a specific surface area can reach 80 to 100m<2>/g. The present invention has the advantages of no solvent use, no waste liquid discharge, simple technological process, low energy consumption, etc., which belongs to environmental-friendly 'green chemistry'.
Description
Technical field
The present invention relates to the preparation method of nano-scale cerium zirconium mixed oxide sosoloid, this sosoloid is mainly used in the raw material of cleaning catalyst for tail gases of automobiles auxiliary agent, fuel cell and function ceramics, and low temperature solid-solid reaction legal system was equipped with the method for nano-scale cerium zirconium mixed oxide sosoloid during the present invention was specifically related to.
Background technology
Along with developing of automobile industry, vehicle exhaust has become the major cause of current urban air pollution, and it has a strong impact on people's healthy and vegeto-animal growth, and catalyzer and the auxiliary agent of therefore studying excellent property are most important.Nano-scale cerium Zirconium oxide sosoloid is a kind of good cleaning catalyst for tail gases of automobiles auxiliary agent, because its adding, not only reduced the usage quantity of precious metal in the catalyzer, and increased its oxygen storage capacity and physical strength, thermostability and catalytic activity are improved.
The method of synthesis nano cerium zirconium compound oxide sosoloid mainly contains at present: high temperature solid phase synthesis, wet chemistry method (comprising common hydrothermal method, coprecipitation method, sol-gel method, microemulsion method etc.).They respectively have relative merits: though high temperature solid phase synthesis technology is simple, product granularity is big, must can reach nano level through mechanical workouts such as comminution by gas stream, and power consumption; The cerium zirconium compound oxide solid-solution particles crystal grain of Hydrothermal Preparation is grown complete, good crystalline and controlled amount, and particle purity height, good dispersity, the little narrow distribution range of particle diameter, but cost is than higher; Coprecipitation method makes metal salt concentrations remain on lower level always, helps the crystal grain nucleation, has suppressed the growth of particle, and each uniform component distribution of coprecipitation method is added different stablizers and can be made the variation of preparation particle crystal formation; The product good uniformity that sol-gel method makes, the crystal grain radius is little, and specific surface area is big, shortcoming is that organic solvent is poisonous and need high-temperature calcination easily cause reunion, and technical process is longer, and all wet-chemical prepare technology and all exist waste liquid amount big, do not meet the requirement of Green Chemistry.
Patent CN1387943 discloses a kind of preparation technology who adopts the precipitator method to prepare cerium oxide and zirconium white composite oxide solid solution, this composite oxide solid solution comprises cerium oxide 10～90% (mol%), zirconium white 10～90% (mol%), it is characterized in that mixed reactant is behind alkali precipitation, throw out thermal treatment, oven dry, calcining are made, be at least 35m in the specific surface area of calcining after 6 hours under 1000 ℃
2/ g, and exist with the pure sosoloid form of cerium oxide in zirconium white.
Patent US2004087440 discloses the composite oxide solid solution that adopts sol-gel method and Preparation by Uniform Precipitation cerium-zirconium composite oxide sosoloid and mix again other rare earth, alkaline earth element, and being used for cleaning catalyst for tail gases of automobiles can use under 1000 ℃ or higher temperature.Calcined 5 hours down at 800 ℃, specific surface area is at 28～59m
2/ g.
K.Eguchi, N.Akasaka, H.Mitsuyasu, what several people of Y.Nonaka adopted in paper " Process ofsolid state reaction between doped ceria and zirconia " is high temperature solid phase synthesis, gained cerium zirconium compound oxide sosoloid (but wherein also doped with yttrium) is to make under 1100～1700 ℃ temperature, and the particle diameter of gained particle is at 250～400nm.
Summary of the invention
What the present invention prepared the employing of cerium zirconium compound oxide sosoloid is a kind of novel process---middle low temperature solid-solid reaction method, it has does not use solvent, no discharging of waste liquid, simple, the low power consumption and other advantages of technological process, belongs to environment amenable " Green Chemistry ".
Low temperature solid-solid reaction legal system was equipped with nano-scale cerium zirconium mixed oxide sosoloid during the present invention adopted, the crystallization degree height, and crystalline form is the isometric system of rule, granularity 20～70nm, specific surface area reaches 80～100m
2/ g.
The present invention is a kind of preparation technology based on cerium oxide and zirconic nano level composite oxide solid solution, this composite oxide solid solution comprises cerium oxide 90～40% (wt%), zirconium white 10-60% (wt%), utilize cerous carbonate, zirconium carbonate to be raw material, add the oxalic acid mixing in proportion and make through ball milling, calcining, the oxalic acid amount adds by stoichiometric ratio.
Low temperature solid-solid reaction synthesis method prepares the method for nano-scale cerium zirconium mixed oxide sosoloid in of the present invention, comprises the steps:
1) is raw material with cerous carbonate and zirconium carbonate, adds oxalic acid, allow it mix by stoichiometric ratio;
2) mixture being put into ball mill carries out obtaining precursor behind the ball milling;
3) precursor is calcined down at 300～500 ℃, obtained the nano-scale cerium zirconium mixed oxide sosoloid of cube crystal phase structure.
Above-mentioned steps 1) proportional quantity of cerous carbonate and zirconium carbonate calculates by desired cerium oxide of the finished product and zirconic mass ratio and adds in, and the add-on of oxalic acid adds by stoichiometric value.
Above-mentioned steps 1) cerous carbonate and zirconium carbonate use industrial raw material in.
Above-mentioned steps 2) the ball milling time is 30～60 minutes in, and the rotating speed of ball mill is 90～200 rev/mins.
Above-mentioned steps 3) calcination time is 3～5 hours.
The nano-scale cerium zirconium mixed oxide sosoloid that the present invention obtained, granularity are that specific surface area reaches 80～100m between 20～40nm
2/ g, the specific surface area after 1000 ℃ calcining was worn out in 6 hours down is at least at 30m
2/ g.
XRD characterizes proof: cerium zirconium compound oxide crystal formation of the present invention is a cubic, is to exist with the complete solid solution form.
The specific surface area of indication of the present invention refers to the BET specific surface area.
Beneficial effect of the present invention is:
1. catalyzer good dispersity, the specific surface area height that obtains by middle low temperature solid-solid reaction method exists with the composite oxide solid solution form.
2. the crystalline phase of catalyzer is a cube crystalline phase.
3. have and do not use solvent, no discharging of waste liquid, simple, the low power consumption and other advantages of technological process, meet the Green Chemistry requirement.
Description of drawings
Fig. 1 is a process flow sheet of the present invention
Fig. 2 is an XRD figure of the present invention
Embodiment
Specific examples:
1, takes by weighing zirconium carbonate 10g, cerous carbonate 70.16g, oxalic acid 88.80g allows it mix, put into and carry out ball milling in the ball mill, rotating speed is 90 rev/mins, 60 minutes time, and the precursor that obtains is calcined, 300 ℃ of calcinings of calcining temperature 5 hours, the product that obtains is the nano cerium zirconium oxide compound, median size 30～40nm.
2, take by weighing zirconium carbonate 10g, cerous carbonate 23.40g, oxalic acid 37.57g allows it mix, put into and carry out ball milling in the ball mill, rotating speed is 90 rev/mins, 60 minutes time, and the precursor that obtains is calcined, 300 ℃ of calcinings of calcining temperature 3 hours, the product that obtains is the nano cerium zirconium oxide compound, median size 20～40nm.
3, take by weighing zirconium carbonate 10g, cerous carbonate 11.69g, oxalic acid 24.75g allows it mix, put into and carry out ball milling in the ball mill, rotating speed is 150 rev/mins, 45 minutes time, and the precursor that obtains is calcined, 400 ℃ of calcinings of calcining temperature 4 hours, the product that obtains is a nanometer cerium zirconium oxide sosoloid, median size 40～60nm.
4, take by weighing zirconium carbonate 10g, cerous carbonate 7.80g, oxalic acid 20.47g allows it mix, put into and carry out ball milling in the ball mill, rotating speed is 180 rev/mins, 40 minutes time, and the precursor that obtains is calcined, 500 ℃ of calcinings of calcining temperature 5 hours, the product that obtains is a nanometer cerium zirconium oxide sosoloid, median size 60～70nm.
5, take by weighing zirconium carbonate 10g, cerous carbonate 5.20g, oxalic acid 17.63g allows it mix, put into and carry out ball milling in the ball mill, rotating speed is 200 rev/mins, 30 minutes time, and the precursor that obtains is calcined, 500 ℃ of calcinings of calcining temperature 3 hours, the product that obtains is a nanometer cerium zirconium oxide sosoloid, median size 50～60nm.
Claims (5)
- In one kind low temperature solid-Gu reaction synthesis method prepares the method for nano-scale cerium zirconium mixed oxide sosoloid, it is characterized in that comprising the steps:1) is raw material with cerous carbonate and zirconium carbonate, adds oxalic acid, allow it mix by stoichiometric ratio;2) mixture being put into ball mill carries out obtaining precursor behind the ball milling;3) precursor is calcined down at 300～500 ℃, obtained the nano-scale cerium zirconium mixed oxide sosoloid of cube crystal phase structure.
- 2. in according to claim 1 low temperature solid-Gu reaction synthesis method prepares the method for nano-scale cerium zirconium mixed oxide sosoloid, it is characterized in that above-mentioned steps 1) in the proportional quantity of cerous carbonate and zirconium carbonate calculate by desired cerium oxide of the finished product and zirconic mass ratio and add, the add-on of oxalic acid adds by stoichiometric value.
- Solid 3. according to claim 1 in low temperature solid-reaction synthesis method prepares the method for nano-scale cerium zirconium mixed oxide sosoloid, it is characterized in that above-mentioned steps 1) in cerous carbonate and zirconium carbonate use industrial raw material.
- Solid 4. according to claim 1 in low temperature solid-reaction synthesis method prepares the method for nano-scale cerium zirconium mixed oxide sosoloid, it is characterized in that above-mentioned steps 2) the middle ball milling time is 30～60 minutes, the rotating speed of ball mill is 90～200 rev/mins.
- Solid 5. according to claim 1 in low temperature solid-reaction synthesis method prepares the method for nano-scale cerium zirconium mixed oxide sosoloid, it is characterized in that above-mentioned steps 3) middle calcination time is 3～5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100514340A CN100334001C (en) | 2004-09-13 | 2004-09-13 | Medium-low temperature solid-solid reaction method for preparing nano grade cerium-zirconium composite oxide solid solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100514340A CN100334001C (en) | 2004-09-13 | 2004-09-13 | Medium-low temperature solid-solid reaction method for preparing nano grade cerium-zirconium composite oxide solid solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1749171A CN1749171A (en) | 2006-03-22 |
| CN100334001C true CN100334001C (en) | 2007-08-29 |
Family
ID=36604853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100514340A Expired - Fee Related CN100334001C (en) | 2004-09-13 | 2004-09-13 | Medium-low temperature solid-solid reaction method for preparing nano grade cerium-zirconium composite oxide solid solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100334001C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844807B (en) * | 2010-05-17 | 2012-04-25 | 山东理工大学 | Preparation method of platy hafnium oxide nano powder |
| CN102167403B (en) * | 2011-02-28 | 2013-05-22 | 中国科学院宁波材料技术与工程研究所 | Preparation method of composite metallic oxide powder |
| CN104591275B (en) * | 2014-12-30 | 2016-05-18 | 四川大学 | Aqueous medium disperses the synthetic method of cerium Zirconium oxide nano material |
| CN112724836B (en) * | 2020-12-24 | 2022-03-29 | 德米特（苏州）电子环保材料有限公司 | Cerium-zirconium-doped polishing solution and preparation method and application thereof |
| CN112808260B (en) * | 2020-12-28 | 2023-10-20 | 江门市科恒实业股份有限公司 | Method for preparing cerium-zirconium solid solution by ball milling method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5712218A (en) * | 1992-12-21 | 1998-01-27 | Rhone-Poulenc Chimie | Cerium/zirconium mixed oxide catalysts having high/stable specific surface areas |
| CN1094467C (en) * | 1999-02-15 | 2002-11-20 | 上海跃龙有色金属有限公司 | Nm-class compound Ce-Zr oxide and its preparing process and application |
| CN1493519A (en) * | 2002-10-29 | 2004-05-05 | 北京有色金属研究总院 | Preparation of cerium zirconium composite oxide using coprecipitation-high pressure water heat combining method |
-
2004
- 2004-09-13 CN CNB2004100514340A patent/CN100334001C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5712218A (en) * | 1992-12-21 | 1998-01-27 | Rhone-Poulenc Chimie | Cerium/zirconium mixed oxide catalysts having high/stable specific surface areas |
| CN1094467C (en) * | 1999-02-15 | 2002-11-20 | 上海跃龙有色金属有限公司 | Nm-class compound Ce-Zr oxide and its preparing process and application |
| CN1493519A (en) * | 2002-10-29 | 2004-05-05 | 北京有色金属研究总院 | Preparation of cerium zirconium composite oxide using coprecipitation-high pressure water heat combining method |
Non-Patent Citations (1)
| Title |
|---|
| 低温合成纳米级固溶体Ce1-xZrxO2的研究 冯长根等，硅酸盐学报，第32卷第4期 2004 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1749171A (en) | 2006-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6162530A (en) | Nanostructured oxides and hydroxides and methods of synthesis therefor | |
| CN106848231B (en) | Compound prepared by composite precursor preparation method and battery comprising compound | |
| CN101745375B (en) | Cerium zirconium aluminum based multiple oxide material and preparing method thereof | |
| KR101854708B1 (en) | Complexometric precursor formulation methodology for industrial production of fine and ultrafine powders and nanopowders of lithium metal oxides for battery applications | |
| CA2905984C (en) | Complexometric precursor formulation methodology for industrial production of fine and ultrafine powders and nanopowders of lithium metal oxides for battery applications | |
| CN101767770A (en) | Method for preparing ZrO2-CeO2/CNTs composite nanotube by hydrothermal method | |
| CN105948098A (en) | Spherical lanthanum oxide | |
| CN100334001C (en) | Medium-low temperature solid-solid reaction method for preparing nano grade cerium-zirconium composite oxide solid solution | |
| JP4928931B2 (en) | Ceria-zirconia composite oxide and method for producing the same | |
| EP1792873A1 (en) | Nanostructured oxides and hydroxides and methods of synthesis therefor | |
| JP2012236741A (en) | Ceria-zirconia composite oxide nanoparticle having bar shape |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070829 Termination date: 20091013 |