CN1369460A - Process for preparing Ce-Zr based composite oxide - Google Patents
Process for preparing Ce-Zr based composite oxide Download PDFInfo
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- CN1369460A CN1369460A CN 02104435 CN02104435A CN1369460A CN 1369460 A CN1369460 A CN 1369460A CN 02104435 CN02104435 CN 02104435 CN 02104435 A CN02104435 A CN 02104435A CN 1369460 A CN1369460 A CN 1369460A
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Abstract
A composite Ce-Zr based oxide is preparedf rom nitrate through precipitation by using ammonium bicarbonate as precipitant, chemical reaction, drying and calcine. It can be used as co-catalyst with high power to absorb and release oxygen. Its advantages are high specific surface are and high oxygen bearing power.
Description
Technical field:
The present invention relates to a kind of preparation method with cerium oxide and zirconic a kind of Ce-Zr based composite oxide of high-specific surface area and high oxygen storage power.Its preparation method is raw material with nitrate, makes through processes such as precipitation, drying, roastings.
Background technology:
In vehicle exhaust was handled, the three-way catalyst of using was a multi-component compound catalyzer at present.Three-way catalyst can be with the carbon monoxide in the vehicle exhaust, hydrocarbon polymer and oxynitrides.Purify simultaneously, wherein the purification of carbon monoxide and hydrocarbon polymer is to realize and oxynitrides is to realize by reduction reaction that by oxidizing reaction this requires catalyzer to have and store oxygen preferably, discharges the oxygen ability.Cerium in the catalyzer, zirconium mixed oxide (can contain a small amount of other component) can play the effect that this stores oxygen, discharges oxygen.
The preparation of cerium zirconium compound oxide requires high temperature solid state reaction stage of experience.High temperature causes specific surface area to descend, and the reaction of the catalytic purification of vehicle exhaust is carried out on catalyst surface, and this just requires catalyzer to have big specific surface area.So the preparation of bigger serface cerium zirconium compound oxide is the technology that has much practical value.
Among Te Kaiping 6-279027 and the special fair 8-16015 zirconium solution and cerium colloidal sol are mixed, add alkali and obtain throw out.Document record, specific surface area is 15m after 1000 ℃ of calcinings
2/ g.
Mixture with the compound of median size 0.05-0.3um and hydrous zirconia sol below the crystallite diameter 4nm and cerium among the Te Kaiping 5-116945 burns till, and makes mixed oxide.Document record, specific surface area is 15m after 850 ℃ of calcinings
2/ g.
Among the CN1193948A with Zircosol ZN (xln or obtain by in zirconium carbonate, adding nitric acid) solution and cerium (IV) compound, mixture heats being higher than under 100 ℃ the temperature, by heating, resulting reaction mixture is transferred to alkaline ph value, reclaim the throw out of this acquisition. according to document record, specific surface area is 30m after 900 ℃ of calcinings
2/ g.
With Zircosol ZN (xln or obtain by add nitric acid in zirconium carbonate) solution and cerium (IV) compound, this mixture heats under 150 ℃ temperature among the CN12222127A, transfers to the mixture pH value and is the reheat processing of alkalescence back and obtains throw out.According to document record, specific surface area is 39m after 900 ℃ of calcinings
2/ g, oxygen storage capacity are 2.0mmol/g.
Joul.catal.1997 has reported the cerium zirconium compound oxide that makes with high-energy ball milling method among the 169:490-502, its specific surface area is at 16-20m
2Between/the g.
Above-mentioned preceding two kinds of preparation methods, the products obtained therefrom specific surface area is less.Several preparation methods' in back cost is higher and the operating time is long.For example: in the method for using zirconia sol, the hydrolysis time of zirconium saline solution was above 100 hours; Needing the hold-time after Zircosol ZN and the adjustment of cerium (IV) strength of solution finish be 6 hours.
Decomposition method (spy opens flat 11-165067) can make cerium zirconium compound oxide in organic reagent complexing-thermal decomposition method (spy opens flat 9-40425) and organic acid precipitation-inertia or the non-oxidizing atmosphere.But this method production cost is high and produce waste gas, pollutes.
Sol-gel method (Journal of Molecular Catalysis, 2000, the cerium zirconium compound oxide that 14:81) makes, though simple, the specific surface area of cerium zirconium compound oxide is little.According to document record, specific surface area is 40.6m after 600 ℃ of calcinings
2/ g.
Summary of the invention:
The object of the present invention is to provide a kind of preparation method who can be made into the cerium zirconium compound oxide of the cerium zirconium compound oxide sosoloid that specific surface area is big, oxygen storage capacity is high.Purpose of the present invention is realized by following technical scheme: the preparation method of Ce-Zr based composite oxide is a raw material with nitrate, makes through processes such as precipitation, drying, roastings, by forming expression Ce
1-x-yZr
xB
yO
2-δ, the nitrate that contains Ce (III), Zr and metallic element B of getting stoichiometric ratio is water-soluble, makes solution (I), gets the water-soluble solution (II) of making of ammonium hydrogencarbonate or carbonic acid ammonia, and solution (I) is mixed with solution (II), carries out chemical reaction.; After this reaction is carried out 5-30 minute, add ammoniacal liquor, the pH value of mixing solutions is between 3-6 behind the control adding ammoniacal liquor, and this process forms flocks; After stirring 2--10 hour under the room temperature static heavyization 2--12 hour again, with the solution after static heavyization in still air 30 ℃--drying under 70 ℃ of temperature, at 400 ℃--in 1000 ℃ the temperature range roasting 2--4 hour, can get cerium zirconium compound oxide.
Described Ce
1-x-yZr
xB
yO
2-δ, wherein B is Ca or Sr or Ba or Mn or Al or Si or the arbitrary rare earth element except that Ce, x 0.10-0.75, y at 0.00-0.10, δ between 0.00-0.30.
Described rare earth is meant that by period of element atom ordinal number be element in the group formed of 57 to 71 element and yttrium.
Advantage of the present invention is: in the X-ray diffraction spectrogram with the cerium zirconium compound oxide composition that a process for preparing, pure zirconia cerium or pure zirconia diffraction peak do not occur, illustrate to form single homogeneous phase sosoloid.Be that described cerium zirconium compound oxide is not cerium oxide and zirconic simple admixture, but formed the material of composite oxides or sosoloid.When using these composite oxides, demonstrate high oxygen and absorb and releasability as promotor.This method is a raw material with nitrate, is precipitation agent with the ammonium hydrogencarbonate, through chemical reaction, drying, roasting etc.This method cost is low simultaneously.
Embodiment:
Embodiment 1:
This example explanation general formula is Ce
0.5Zr
0.5O
2The preparation of mixed oxide.
To produce 30g Ce
0.5Zr
0.5O
2Sosoloid is benchmark.(1) gets 44gCe (NO
3)
36H
2O, 44g Zr (NO
3)
45H
2O and 490ml deionized water are made solution (I); Get 635ml, 0.4mol/l NH
4HCO
3Solution (II). solution (I) is splashed in the solution (II), and in the dropping process, pH value constantly reduces, and treats to change dropping ammonia solution after solution (I) drips off, and keeps PH in 4 ± 0.5 scopes; Generate white flocks this moment, stirred this precipitation at ambient temperature 4 hours; (2) static heavyization of solution spent the night, then solution is placed 60 ℃ of still airs dry, 500 ℃ of roastings can get product in 2 hours.Product is single cerium zirconium compound oxide sosoloid, and specific surface area is 47m
2/ g, oxygen storage capacity are 0.34mmol/g.
Embodiment 2:
With example explanation general formula is Ce
0.495Zr
0.495Pr
0.01O
2The preparation of mixed oxide.
With 43.6g Ce (NO
3)
36H
2O, 43.1gZr (NO
3)
45H
2O, 0.35gPr
6O
11Make solution (I) with the 507ml deionized water.Get 627ml 0.4mol/l NH
4HCO
3Solution is made solution (II).Solution (I) is splashed in the solution (II), and in the dropping process, pH value constantly reduces, treat that solution (I) drips off after, change dropping ammonia solution, and keep PH in 5 ± 0.5 scopes; Generate white flocks this moment, stirred this precipitation at ambient temperature 2 hours; (2) static heavyization of solution spent the night, then solution is placed 60 ℃ of still airs dry, 500 ℃ of roastings can get product in 2 hours.Operation steps subsequently is as embodiment 1.Product is single Ce-Zr based composite oxide sosoloid, and specific surface area is 45m
2/ g, oxygen storage capacity are 0.36mmol/g.
Embodiment 3:
With example explanation general formula is Ce
0.45Zr
0.45Pr
0.1O
2The preparation of mixed oxide.
With 39g Ce (NO
3)
36H
2O, 38.6gZr (NO
3)
45H
2O, 3.4gPr
6O
11Make solution (V) with the 499ml deionized water.Get 562ml 0.4mol/l NH
4HCO
3Solution is made solution (VI).Solution (V) is splashed in the solution (VI), and in the dropping process, pH value constantly reduces, treat that solution (I) drips off after, change dropping ammonia solution, and keep PH in 3 ± 0.5 scopes; Generate white flocks this moment, stirred this precipitation at ambient temperature 3 hours; (2) static heavyization of solution spent the night, then solution is placed 60 ℃ of still airs dry, 500 ℃ of roastings can get product in 2 hours.Operation steps subsequently is as embodiment 1.Product is single Ce-Zr based composite oxide sosoloid, and specific surface area is 44m
2/ g, oxygen storage capacity are 0.37mmol/g.
Embodiment 4:
With example explanation general formula is Ce
0.75Zr
0.25O
2The preparation of mixed oxide.
With 61g Ce (NO
3)
36H
2O, 20gZr (NO
3)
45H
2O and 469ml deionized water are made solution (VII).Get 645ml 0.4mol/l NH
4HCO
3Solution is made solution (VIII).Solution (VII) is splashed in the solution (VIII), and in the dropping process, pH value constantly reduces, treat that solution (I) drips off after, change dropping ammonia solution, and keep PH in 4 ± 0.5 scopes; Generate white flocks this moment, stirred this precipitation at ambient temperature 3.5 hours; (2) static heavyization of solution spent the night, then solution is placed 60 ℃ of still airs dry, 500 ℃ of roastings can get product in 2 hours.Operation steps subsequently is as embodiment 1.Product is single cerium zirconium compound oxide sosoloid, and specific surface area is 40m
2/ g, oxygen storage capacity are 0.41mmol/g.
The oxygen storage capacity of cerium zirconium compound oxide of the present invention is to store the ability that discharges oxygen in oxygen, the reducing environment with it in well-oxygenated environment to estimate.Continuous cerium oxide and zirconium oxide composite oxides of this test evaluation pulse oxygen and the ability that consumes pulse oxygen.Vector gas is that flow velocity is the pure helium of 30 ml/min.The pulse of oxygen purity oxygen.Use thermal conductivity detector to come analytical gas by chromatography.Quantity by the oxygen that consumes can be measured oxygen storage capacity.The eigenwert of oxygen storage capacity is represented with the mmole number of every gram product intussusception oxygen, is measured under 427 ℃.
Claims (3)
1, a kind of preparation method of Ce-Zr based composite oxide is a raw material with nitrate, makes through processes such as precipitation, drying, roastings, it is characterized in that, by forming expression Ce
1-x-yZr
xB
yO
2-δ, the nitrate that contains Ce (III), Zr and metallic element B of getting stoichiometric ratio is water-soluble, makes solution (I), gets the water-soluble solution (II) of making of ammonium hydrogencarbonate or carbonic acid ammonia, and solution (I) is mixed with solution (II), carries out chemical reaction.; After reaction is carried out 5-30 minute, add ammoniacal liquor, the pH value of mixing solutions is between 3-6 behind the control adding ammoniacal liquor, and this process forms flocks; After stirring 2--10 hour under the room temperature static heavyization 2--12 hour again, with the solution after static heavyization in still air 30 ℃--drying under 70 ℃ of temperature, at 400 ℃--in 1000 ℃ the temperature range roasting 2--4 hour, can get cerium zirconium compound oxide.
2, a kind of preparation method of a kind of Ce-Zr based composite oxide according to claim 1 is characterized in that described Ce
1-x-yZr
xB
yO
2-δ, wherein B is Ca or Sr or Ba or Mn or Al or Si or the arbitrary rare earth element except that Ce, x 0.10-0.75, y at 0.00-0.10, δ between 0.00-0.30.
3, a kind of preparation method of a kind of Ce-Zr based composite oxide according to claim 1 is characterized in that described rare earth is meant that by atomicity in the periodic table of elements be element in the group formed of 57 to 71 element and yttrium.
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100374374C (en) * | 2005-08-28 | 2008-03-12 | 内蒙古科技大学 | Preparation method of high specific surface area nano-cerium oxide |
| CN100376484C (en) * | 2003-12-30 | 2008-03-26 | 同济大学 | Preparation method of nano cerium zirconium compound oxide and its application |
| CN100491258C (en) * | 2004-03-17 | 2009-05-27 | 罗狄亚化学公司 | Composition based on zirconium, cerium and tin oxides, preparation and its use as catalyst |
| CN101074490B (en) * | 2007-06-15 | 2011-05-04 | 北京工业大学 | Method for producing spherical, tie-shaped and octahedral polycrystalline Ce0.6Zr0.3Y0.1O2 particles of um sizes |
| CN101544392B (en) * | 2008-03-26 | 2011-05-25 | 比亚迪股份有限公司 | Preparation method for cerium-zirconium-oxygen solid solution |
| CN102134088A (en) * | 2011-02-01 | 2011-07-27 | 大连海事大学 | Penniform large-grain cerium-based composite oxide powder with high specific surface area and preparation method thereof |
| CN102134089A (en) * | 2011-02-01 | 2011-07-27 | 大连海事大学 | Fusiform large-scale cerium based composite oxide powder and preparation method thereof |
| CN102161496A (en) * | 2011-02-01 | 2011-08-24 | 大连海事大学 | Preparation method of high-dispersibility spherical cerium-based composite oxide powder |
| CN101595060B (en) * | 2007-02-02 | 2011-12-21 | 旭硝子株式会社 | Method for producing solid solution fine particle |
| CN102416315A (en) * | 2010-09-28 | 2012-04-18 | 北京有色金属研究总院 | Magnesium-containing rare earth oxygen storage material and preparation method thereof |
| CN102417352A (en) * | 2010-09-28 | 2012-04-18 | 北京有色金属研究总院 | Preparation method of zirconium-containing rare earth composite oxide |
| CN102513089A (en) * | 2011-12-14 | 2012-06-27 | 上海华明高纳稀土新材料有限公司 | Preparation method of cerium-zirconium-based oxide solid solution with high specific surface area |
| CN102698731A (en) * | 2012-05-08 | 2012-10-03 | 赣州博晶科技有限公司 | Preparation method of high temperature resistant cerium zirconium solid solution |
| CN101250056B (en) * | 2008-03-18 | 2013-01-02 | 中国科学院上海硅酸盐研究所 | Method for low-temperature preparation of pure phase oxide material |
| CN101998933B (en) * | 2008-02-12 | 2013-04-03 | 株式会社三德 | Composite oxide |
| CN103182302A (en) * | 2011-12-28 | 2013-07-03 | 北京有色金属研究总院 | Rare earth zirconium-based composite oxide with core-shell structure, and preparation method and application thereof |
| CN109351355A (en) * | 2018-10-17 | 2019-02-19 | 台州欧信环保净化器有限公司 | A kind of Motorcycle catalytic converter and preparation method thereof meeting motorcycle state four standard |
| CN113813953A (en) * | 2021-07-21 | 2021-12-21 | 浙江大学 | Preparation and application methods of cerium-zirconium composite oxide solid solution catalyst |
-
2002
- 2002-03-18 CN CN 02104435 patent/CN1369460A/en active Pending
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100376484C (en) * | 2003-12-30 | 2008-03-26 | 同济大学 | Preparation method of nano cerium zirconium compound oxide and its application |
| CN100491258C (en) * | 2004-03-17 | 2009-05-27 | 罗狄亚化学公司 | Composition based on zirconium, cerium and tin oxides, preparation and its use as catalyst |
| CN100374374C (en) * | 2005-08-28 | 2008-03-12 | 内蒙古科技大学 | Preparation method of high specific surface area nano-cerium oxide |
| CN101595060B (en) * | 2007-02-02 | 2011-12-21 | 旭硝子株式会社 | Method for producing solid solution fine particle |
| CN101074490B (en) * | 2007-06-15 | 2011-05-04 | 北京工业大学 | Method for producing spherical, tie-shaped and octahedral polycrystalline Ce0.6Zr0.3Y0.1O2 particles of um sizes |
| CN101998933B (en) * | 2008-02-12 | 2013-04-03 | 株式会社三德 | Composite oxide |
| CN101250056B (en) * | 2008-03-18 | 2013-01-02 | 中国科学院上海硅酸盐研究所 | Method for low-temperature preparation of pure phase oxide material |
| CN101544392B (en) * | 2008-03-26 | 2011-05-25 | 比亚迪股份有限公司 | Preparation method for cerium-zirconium-oxygen solid solution |
| CN102417352A (en) * | 2010-09-28 | 2012-04-18 | 北京有色金属研究总院 | Preparation method of zirconium-containing rare earth composite oxide |
| CN102416315A (en) * | 2010-09-28 | 2012-04-18 | 北京有色金属研究总院 | Magnesium-containing rare earth oxygen storage material and preparation method thereof |
| CN102161496A (en) * | 2011-02-01 | 2011-08-24 | 大连海事大学 | Preparation method of high-dispersibility spherical cerium-based composite oxide powder |
| CN102161496B (en) * | 2011-02-01 | 2012-08-22 | 大连海事大学 | Preparation method of high-dispersibility spherical cerium-based composite oxide powder |
| CN102134089B (en) * | 2011-02-01 | 2012-11-07 | 大连海事大学 | Fusiform large-scale cerium based composite oxide powder and preparation method thereof |
| CN102134089A (en) * | 2011-02-01 | 2011-07-27 | 大连海事大学 | Fusiform large-scale cerium based composite oxide powder and preparation method thereof |
| CN102134088A (en) * | 2011-02-01 | 2011-07-27 | 大连海事大学 | Penniform large-grain cerium-based composite oxide powder with high specific surface area and preparation method thereof |
| CN102513089A (en) * | 2011-12-14 | 2012-06-27 | 上海华明高纳稀土新材料有限公司 | Preparation method of cerium-zirconium-based oxide solid solution with high specific surface area |
| CN103182302A (en) * | 2011-12-28 | 2013-07-03 | 北京有色金属研究总院 | Rare earth zirconium-based composite oxide with core-shell structure, and preparation method and application thereof |
| CN102698731A (en) * | 2012-05-08 | 2012-10-03 | 赣州博晶科技有限公司 | Preparation method of high temperature resistant cerium zirconium solid solution |
| CN102698731B (en) * | 2012-05-08 | 2016-07-13 | 赣州博晶科技有限公司 | A kind of preparation method of high temperature resistant cerium zirconium solid solution |
| CN109351355A (en) * | 2018-10-17 | 2019-02-19 | 台州欧信环保净化器有限公司 | A kind of Motorcycle catalytic converter and preparation method thereof meeting motorcycle state four standard |
| CN113813953A (en) * | 2021-07-21 | 2021-12-21 | 浙江大学 | Preparation and application methods of cerium-zirconium composite oxide solid solution catalyst |
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