CN101200371A - Composite oxide sosoloid based on cerium oxide and zirconia and method for preparing the same - Google Patents
Composite oxide sosoloid based on cerium oxide and zirconia and method for preparing the same Download PDFInfo
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Abstract
The invention discloses a composite oxide solid solution based on cerium oxide and zirconium oxide and preparation method, wherein the cerium/zirconium atom ratio is at least 1, the preparation method is as follows: first the cerium-containing rare-earth solution and the zirconium solution are mixed according to the proportion, and then organic acid is added according to chemical measurement for even mixing, and then a polymer monomer and initiator, simultaneously one or several surfactants are added, rapid stirring and emulsifying is performed to form water-in-oil emulsion. The emulsion is placed at a certain temperature and generates reaction for a length of time so as to be polymerized to form the gel, the gel is dried and roasted to obtain rare-earth-zirconium solid solution. The invention is a preparation method different with the prior technique, and has simple process, moreover the prepared composite oxide solid solution has larger specific surface area and higher oxygen storage amount.
Description
Technical field
The present invention relates to a kind of based on cerium oxide and zirconic composite oxide solid solution and preparation method thereof, relate in particular to a kind of be used for cleaning catalyst for tail gases of automobiles and other catalytic material based on cerium oxide and zirconic composite oxide solid solution.
Background technology
Along with the increasingly stringent of legislations of environmental protection in the world wide, it is more and more important to be used to the catalytic conversion technique handled with purifying automobile tail gas.At present, the measure of improvement is divided into emission controls by improving combustion and external purification.External purification mainly is to realize by the purifying vehicle exhaust catalytic unit, and the core of purifying vehicle exhaust catalytic unit is a catalyzer.Polyfunctional catalyst should be understood to mean catalyzer not only can carry out oxidation (carbon monoxide that exists in the tail gas and hydrocarbon polymer particularly), but also can reduce (being present in the oxynitride in the tail gas particularly equally) promptly so-called " three-way catalyst ".
Particularly important and what play a key effect is cerium oxide and two kinds of components of zirconium white in this type catalyst now.The rare earth zirconium mixed oxide sosoloid of the high-specific surface area of high-temperature stable is a kind of catalyst aid of good purifying vehicle exhaust, because its adding, not only reduced the consumption of precious metal in the catalyzer, and improved catalytic activity, oxygen storage capacity, selectivity and thermostability, enlarged the air-fuel ratio operation window.
With regard to validity, described catalyzer at first must even at high temperature have high-specific surface area.Cerium has surge capability to the oxygen level variation of gaseous mixture to be processed in addition, and the sort buffer ability is estimated with oxygen storage capacity in well-oxygenated environment and the oxygen storage capacity again in reducing environment.But this oxygen storage capacity reduces in high temperature so that the conversion of three kinds of pollutents is abundant inadequately.
Chinese patent publication number CN1193948 discloses a kind of based on cerium oxide and zirconic composition, Preparation Method And The Use, it is characterized by the mixture that will comprise zirconium compounds and cerium (IV) compound and heats being higher than under 100 ℃ the temperature.It is at least 30m in the specific surface area of calcining after 6 hours under 900 ℃
2/ g and it are to be provided with the pure sosoloid form of cerium oxide in zirconium white.
Chinese patent publication number CN1255105 disclose a kind of have improved thermostability and oxygen storage volume based on cerium oxide and zirconic preparation of compositions method, it is characterized by first oxyhydroxide presoma and carry out hydrothermal treatment consists at 90 ℃～200 ℃ with cerium and zirconium, add a kind of negatively charged ion or nonionogenic tenside then, obtain having the cerium zirconium sosoloid of improved size distribution, specific surface area, oxygen storage capacity and pore volume.
Though above-mentioned two kinds of methods can obtain the sosoloid of high-specific surface area and high oxygen storage capacity, all must pass through high pressure water thermal treatment, thereby higher to equipment requirements.
Chinese patent publication number CN1263868 discloses a kind of nanometer cerium zirconium oxide, Preparation Method And The Use, the zirconium white of forming the cerium oxide and 1～95% (wt) that comprises 4～98% (wt), its composite oxides are that the precursor decomposition through containing hydrazine or hydrazonium salt obtains under 200～1000 ℃.The specific surface area of this method gained precursor behind 900 ℃ of following roasting 6h is less.
Chinese patent publication number CN1749171 discloses the method that middle low temperature solid-solid reaction legal system is equipped with nano-scale cerium zirconium mixed oxide sosoloid.This method utilizes cerous carbonate, zirconium carbonate to be raw material, adds the oxalic acid mixing in proportion and makes through ball milling, calcining.Do not use advantages such as solvent, no discharging of waste liquid, technology be simple though this method has, yet its aging specific surface area is less.
Chinese patent publication number CN1565722 discloses a kind of high-specific surface area and has got cerium zirconium sosoloid and preparation method thereof.This method makes the high-specific surface area cerium zirconium sosoloid by a certain proportion of cats product of the preceding adding of reaction through precipitation, ageing, washing, drying and roasting.Though this method can obtain the cerium zirconium sosoloid of high specific surface area, yet preparation cost is higher, and generated time is long.
Summary of the invention
The technical issues that need to address of the present invention be disclose a kind of based on cerium oxide and zirconic composite oxide solid solution and preparation method thereof, to overcome the above-mentioned defective that prior art exists.
The present invention is said based on cerium oxide and zirconic composite oxide solid solution, it is characterized in that having general formula:
Ce
xZr
yRE
zO
2；
Wherein RE represents at least a in other rare earth elements, and described other rare earth elements are meant that scandium, yttrium and period of element atom ordinal number are 57 to 71 element, preferred scandium, lanthanum, neodymium, praseodymium or yttrium;
Wherein: when z=0, x is 0.5～0.95, is in particular 0.55～0.9, is more preferably 0.6～0.8, and x+y=1;
When z＞0, z is 0.01～0.3, preferably 0.02～0.2, and the ratio of x/y is in particular 1～9 greater than 1, preferably 1.5～4,, and x+y+z=1.
Of the present invention is mutually single cubic based on cerium oxide and zirconic composite oxide solid solution, 900～1000 ℃ of aging 4～6 hours product granularity 30～50nm, and specific surface area is 30～70m
2/ g.
The feature of the said sosoloid of the present invention is to adopt reverse microemulsion-high-molecular gel method to prepare.Specifically be to contain the water of inorganic species and high polymer monomer oil phase under the effect of tensio-active agent, obtain water-in-oil emulsion by means of high speed shear emulsification, the minute water nuclear that forms makes that gained sosoloid grain fineness number is little, improved the distribution of stablizer, the formation of superpolymer has simultaneously effectively suppressed growing up and sintering of crystal grain under the hot conditions.
Prepare said method, comprise the steps: based on cerium oxide and zirconic composite oxide solid solution
Step (1) adds mixed salt solution with oxygenant, organic acid, polymer monomer, initiator and tensio-active agent, and stirring and emulsifying obtains emulsion;
Said mixed salt solution is the colloidal sol that contains cerium and zirconic nitric acid or hydrochloric acid, and the cerium/atomic percent zirconium of mixed salt solution is 1～9;
The said cerium colloidal sol that contains is the hydrochloric acid soln that contains the salpeter solution of cerous nitrate or contain cerous chlorate, and wherein, cerous nitrate or the volumetric molar concentration that contains cerous chlorate are 0.1～2mol/l;
Said zirconium colloidal sol is the salpeter solution that contains zirconium nitrate, the salpeter solution of Zircosol ZN or the hydrochloric acid soln of basic zirconium chloride, and wherein, the volumetric molar concentration of zirconium nitrate, Zircosol ZN or basic zirconium chloride is 0.1～2mol/l;
Contain that cerium colloidal sol can make according to the prior art mode, containing zirconium solution equally is to be that precursor makes according to the prior art mode with the zirconates, as Chinese patent communique CN1193948A document disclosed method, containing cerium colloidal sol can be single compound colloidal sol, also can be the colloidal sol that contains other rare earth element, described other rare earth element is meant that scandium, yttrium and period of element atom ordinal number are 57 to 71 element, preferred scandium, lanthanum, neodymium, praseodymium or yttrium, the molar ratio of other rare earth element in containing cerium colloidal sol is 0～0.60;
The preferred hydrogen peroxide of said oxygenant, oxygenant consumption and cerium ion mol ratio are 2～10.
Said organic acid is selected from one or both in acetic acid, lauric acid, formic acid, the citric acid, and the molar weight that organic acid adds is m a times of metal ion integral molar quantity in the mixed salt solution, and m preferred 1～5.
Said monomer is selected from vinylbenzene, vinyl acetate, vinylformic acid, methacrylic acid, methyl acrylate, the mix monomer of one or more in methyl methacrylate, butyl acrylate, butyl methacrylate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, divinyl and the kalimeris acid anhydrides etc.The volume ratio of said monomer and mixed salt solution is 1.2～2.5;
Initiator is selected from Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), ammonium persulphate, Potassium Persulphate, dibenzoyl peroxide, dilauroyl peroxide, isopropyl benzene hydroperoxide, peroxyesters or peroxy dicarbonates etc., and initiator amount is the 0.5wt%～2wt% of monomer consumption;
Said tensio-active agent is selected from anhydrous sorbitol oleic acid monoester such as commercially available Arlacel-80, sorbitan fatty acid ester Soxylat A 25-7 such as commercially available tween 20 and tween-80, octyl phenyl Soxylat A 25-7 such as the commercially available OP emulsifying agent and the segmented copolymer of triton x-100, polyvinylpyrrolidone, carboxymethyl cellulose, cetyl trimethylammonium bromide, sodium dodecyl benzenylsulfonate or oxyethane and propylene oxide, and consumption is the 1wt%～10wt% of monomer consumption.
Step (2) with the emulsion of step (1) 40 ℃～100 ℃ polyreactions, reaction times is 2～24h, and gel is with 80～200 ℃ of dryings of gel, 300～1000 ℃ of roastings 1～8 hour, it is said based on cerium oxide and zirconic composite oxide solid solution to obtain the present invention.
The finished product that adopt the present invention to obtain can provide with powder type, also can provide with other form.
The rare earth zirconium mixed oxide sosoloid that adopts the present invention to obtain has a lot of application.They are particularly suitable for the catalytic process of various reactions, the dehydration of for example purifying vehicle exhaust catalysis, catalytic burning, hydrocarbon or other organic compound, hydrogenation, dehydrogenation, desulfurization, dehydrohalogenation, oxychlorination, isomerization, disproportionation, demetalization and methanation or shift reaction etc.
In these purposes of catalyzer, sosoloid of the present invention can be used in combination with precious metal.The character of these metals is known with the technology that is introduced into these sosoloid for this area professional.For example, this metal can be a platinum, rhodium or palladium, and they especially can enter into sosoloid of the present invention by dipping.
In the middle of the purposes of mentioning, handling the waste gas (automobile after-burning catalysis) of discharging from oil-fired vehicle is particularly preferred application.
The present invention obtained based on cerium oxide and zirconic composite oxide solid solution is to obtain with powder type but look particular case and by moulding, in order that obtain particle, ball, right cylinder or the cellular form of various size.This sosoloid can be used to usually at the employed any carrier of catalyst field, and this carrier can be selected from aluminum oxide, titanium oxide, silicon oxide, zeolite, silicate, crystallization silicon aluminium phosphate or crystalline aluminophosphate etc.Sosoloid of the present invention also can be used to comprise in the catalyst system of coating, and this coating has catalytic performance and based on these compositions on for example metal and ceramic monoliths type substrate.Coating itself also can comprise the carrier component of above-mentioned those types.This coating is deposited in suprabasil suspension subsequently and obtains by sosoloid of the present invention being mixed with carrier form.
In this manual and in the further part, specific surface area is interpreted as the BET specific surface area, it by ASTM standard D 3663-78 by determination of nitrogen adsorption.
Sosoloid of the present invention exists with pure sosoloid form, and can be recorded by XRD.
The test specification of tolerance oxygen storage capacity:
Sosoloid the surge capability of oxygen is stored oxygen with it in well-oxygenated environment and in reducing environment the restorative ability estimate.Sosoloid earlier contains 10%H in being diluted in helium
2The mixed gas temperature programmed reduction(TPR), be cooled to 400 ℃ then and carry out O
2The thermal conductivity detector analytical gas is used in the pulse titration.Quantity by the oxygen that consumes can be measured oxygen storage capacity.The eigenwert of oxygen storage capacity is expressed with ml (under the standard temperature and pressure (STP) condition) number of the oxygen of the product of every gram introducing.The oxygen storage capacity observed value that provides later be in retort furnace in 900 ℃ of air the product behind the pre-treatment 6h estimate.
Outstanding feature of the present invention has:
Prepare based on cerium oxide and zirconic composite oxide solid solution crystallization degree height, crystal formation is a cubic, is to exist with the complete solid solution form.Gained sosoloid grain-size is below 30nm, and crystal grain still is stabilized in about 50nm behind 900 ℃ of aging 6h.Gained sosoloid specific surface area is big, the oxygen storage capacity height.
Description of drawings
Accompanying drawing 1 is the XRD figure of the fresh oxide compound of the embodiment of the invention 11 gained sosoloid;
Accompanying drawing 2 is XRD figure of the aging oxide compound of the embodiment of the invention 11 gained sosoloid;
Accompanying drawing 3 is XRD figure of the aging oxide compound of the embodiment of the invention 12 gained sosoloid;
Accompanying drawing 4 is TEM figure (amplifying 100,000 times) of the fresh oxide compound of the embodiment of the invention 12 gained sosoloid;
Accompanying drawing 5 are the fresh oxide compounds of the embodiment of the invention 12 gained sosoloid through 900 ℃ of pyroprocessing after 6 hours the aging oxide compound of gained get TEM figure (amplifying 100,000 times).
Embodiment
Embodiment 1
With cerous chlorate solution 33ml (cerium ion concentration is 1mol/l), zirconium oxychloride solution 11ml (zirconium ion concentration is 1mol/l) and 15ml H
2O
2Mix mixing solutions, add 8.1g formic acid, add 80g high polymer monomer methyl methacrylate and initiator Diisopropyl azodicarboxylate 0.8g after the stirring and dissolving, constantly stir under the room temperature and make the initiator dissolving fully, add the 4g Arlacel-80 then; Stirring and emulsifying.
Emulsion places 60 ℃ of waters bath with thermostatic control, is constantly reacting 8 hours under the agitation condition.Then the gained high-molecular gel was placed 120 ℃ of baking ovens dry 12 hours, and got precursor after the drying and place 500 ℃ of roastings of retort furnace to obtain fresh oxide compound after 2 hours.
Get the fresh oxide compound of part and place 900 ℃ of following roastings of retort furnace to obtain aging oxide compound in 6 hours, testing its aging back specific surface area is 32m
2/ g, oxygen storage capacity are 5.71ml/g.
Embodiment 2
The method identical with embodiment 1, that different is H
2O
2Consumption is 30ml, replaces formic acid with the 14g citric acid, and monomeric species changes vinylbenzene into, and surfactant system changes Arlacel-85 into, and polymerization temperature is 80 ℃, polyreaction 6 hours.The specific surface area of the aging oxide compound of gained is 38m
2/ g, oxygen storage capacity are 7.71ml/g.
Embodiment 3
According to the identical method of embodiment 1, that different is H
2O
2Consumption is 22.5ml, replaces formic acid with 5.5g acetic acid, and initiator is a dibenzoyl peroxide, and polymeric reaction temperature changes 80 ℃ into, polyreaction 12 hours.Get the fresh oxide compound of part and place 900 ℃ of roastings of retort furnace to obtain aging oxide compound in 6 hours, testing its aging specific surface area is 34m
2/ g, oxygen storage capacity are 7.54ml/g.
Embodiment 4
With cerium nitrate solution 33ml (cerium ion concentration is 1mol/l), zirconyl nitrate solution 11ml (zirconium ion concentration is 1mol/l) and 15ml H
2O
2Mix and obtain mixing solutions, add the 14g citric acid, fully add 80g high polymer monomer butyl acrylate and dibenzoyl peroxide 0.8g after the stirring and dissolving, the continuous stirring makes the initiator dissolving fully under the room temperature, add 3.5g Arlacel-85 and 0.5g tween-80 then, fast stirring and emulsifying.Emulsion places 80 ℃ of waters bath with thermostatic control, is constantly reacting 10 hours under the agitation condition.Then the gained high-molecular gel was placed 120 ℃ of baking ovens dry 12 hours, and got precursor after the drying and place 500 ℃ of roastings of retort furnace to obtain fresh oxide compound after 2 hours.Get the fresh oxide compound of part and place 900 ℃ of roastings of retort furnace to obtain aging oxide compound in 6 hours, testing its aging specific surface area is 33m
2/ g, oxygen storage capacity are 7.41ml/g.
Embodiment 5
According to the identical method of embodiment 4, different is to replace citric acid with the 35.2g lauric acid, and high polymer monomer changes vinylbenzene 120g into, and initiator Diisopropyl azodicarboxylate, tensio-active agent are the 8g triton x-100, and polymerization temperature is 60 ℃, polyreaction 6 hours.Place 900 ℃ of roastings of retort furnace to obtain aging oxide compound in 6 hours fresh oxide compound, testing its aging specific surface area is 40m
2/ g, oxygen storage capacity are 7.33ml/g.
Embodiment 6
According to the identical method of embodiment 4, different is that high polymer monomer changes methyl methacrylate into, and initiator is Potassium Persulphate 0.8g, and tensio-active agent is 3g triton x-100 and 1g cetyl trimethylammonium bromide, polyreaction 12 hours.Place 900 ℃ of roastings of retort furnace to obtain aging oxide compound in 6 hours the fresh oxide compound of part of gained, testing its aging specific surface area is 44m
2/ g, oxygen storage capacity are 9.31ml/g.
Embodiment 7
According to the identical method of embodiment 4, different is that high polymer monomer is a vinylbenzene, and initiator is a Potassium Persulphate, and tensio-active agent is 3g triton x-100 and 1g Sodium dodecylbenzene sulfonate, polyreaction 10 hours.Get the fresh oxide compound of part and place 900 ℃ of roastings of retort furnace to obtain aging oxide compound in 6 hours, testing its aging specific surface area is 42m
2/ g, oxygen storage capacity are 7.90ml/g.
According to the identical method of embodiment 4, different is that high polymer monomer is a vinylbenzene, and initiator is an ammonium persulphate, and tensio-active agent is 3g triton x-100 and 1g n-hexyl alcohol, polyreaction 10 hours.Get the fresh oxide compound of part and place 900 ℃ of roastings of retort furnace to obtain aging oxide compound in 6 hours, testing its aging specific surface area is 47m
2/ g, oxygen storage capacity are 7.96ml/g.
Embodiment 9
According to the identical method of embodiment 8, different is that high polymer monomer changes vinylbenzene and each 40g of methyl methacrylate into, and tensio-active agent is 3.5g triton x-100 and 0.5g carboxymethyl cellulose, polyreaction 16 hours.Get the fresh oxide compound of part and place 900 ℃ of roastings of retort furnace to obtain aging oxide compound in 6 hours, testing its aging specific surface area is 49m
2/ g, oxygen storage capacity are 9.60ml/g.
According to the identical method of embodiment 9, different is that tensio-active agent changes 3.5g triton x-100 and 0.5g polyvinylpyrrolidone into, polyreaction 12 hours.Get the fresh oxide compound of part and place 900 ℃ of roastings of retort furnace air to obtain aging oxide compound in 6 hours, testing its aging specific surface area is 42m
2/ g, oxygen storage capacity are 9.31ml/g.
Embodiment 11
According to the identical method of embodiment 9, different is that tensio-active agent is 3.5g triton x-100 and 0.5g segmented copolymer EO
73PO
28EO
73Precursor places 500 ℃ of roastings of retort furnace air to obtain fresh oxide compound after 2 hours, and its XRD figure spectrum is seen accompanying drawing 1.Get the fresh oxide compound of part and place 900 ℃ of roastings of retort furnace to obtain aging oxide compound in 6 hours, testing its aging specific surface area is 52m
2/ g, oxygen storage capacity are 10.71ml/g, and its XRD figure spectrum is seen accompanying drawing 2.
Embodiment 12
Cerium nitrate solution 29ml (cerium ion concentration is 1mol/l) is mixed with zirconyl nitrate solution 11ml (zirconium ion concentration is 1mol/l), getting 0.3787g lanthanum trioxide and 0.2625g yttrium oxide joins in the cerium zirconium mixed solution after with the 10ml nitric acid dissolve, fully mix, in mixing solutions, add 13ml H
2O
2With the 10.5g citric acid, fully add 40g high polymer monomer vinylbenzene, 40g vinyl acetate and initiator ammonium persulfate 0.8g after the stirring and dissolving, stir and make that the initiator dissolving is complete, add 3g triton x-100 and 1g n-hexyl alcohol then, fast stirring and emulsifying.Emulsion places 80 ℃ of waters bath with thermostatic control, is constantly reacting 12 hours under the agitation condition.Then the gained high-molecular gel was placed 120 ℃ of baking ovens dry 12 hours, get precursor after the drying and place 500 ℃ of roastings of retort furnace air to obtain fresh oxide compound after 2 hours, its particle size distribution of transmission electron microscope observation (is seen accompanying drawing 4) between 5～40nm.Get the fresh oxide compound of part and place 900 ℃ of roastings of retort furnace air to obtain aging oxide compound in 6 hours, testing its aging specific surface area is 65m
2/ g, oxygen storage capacity are 12.26ml/g, and its particle size distribution of transmission electron microscope observation (is seen accompanying drawing 5) between 5～50nm, and its XRD figure spectrum is seen accompanying drawing 3.
Claims (10)
1. based on cerium oxide and zirconic composite oxide solid solution, it is as follows to have a general formula:
Ce
xZr
yRE
zO
2；
Wherein RE represents at least a in other rare earth elements;
Wherein: when z=0, x is 0.5～0.95, and x+y=1;
When z＞0, z is 0.01～0.3, and the ratio of x/y is greater than 1, and x+y+z=1.
2. according to claim 1ly it is characterized in that based on cerium oxide and zirconic composite oxide solid solution described other rare earth elements are meant that scandium, yttrium and period of element atom ordinal number are 57 to 71 element.
3. according to claim 2ly it is characterized in that based on cerium oxide and zirconic composite oxide solid solution described other rare earth elements are scandium, lanthanum, neodymium, praseodymium or yttrium.
4. according to claim 1ly it is characterized in that based on cerium oxide and zirconic composite oxide solid solution when z=0, x is 0.55～0.9.
5. according to claim 4ly it is characterized in that based on cerium oxide and zirconic composite oxide solid solution x is 0.6～0.8.
6. according to claim 1ly it is characterized in that when z＞0, z is 0.02～0.2, and the ratio of x/y is 1～9 based on cerium oxide and zirconic composite oxide solid solution.
7. according to claim 1 based on cerium oxide and zirconic composite oxide solid solution, it is characterized in that, of the present invention is mutually single cubic based on cerium oxide and zirconic composite oxide solid solution, 900～1000 ℃ of aging 4～6 hours product granularity 30～50nm, specific surface area is 30～70m
2/ g.
8. prepare each said method of claim 1～7, comprise the steps: based on cerium oxide and zirconic composite oxide solid solution
Step (1) adds mixed salt solution with oxygenant, organic acid, polymer monomer, initiator and tensio-active agent, and stirring and emulsifying obtains emulsion;
Said mixed salt solution is the colloidal sol that contains cerium and zirconic nitric acid or hydrochloric acid, and the cerium/atomic percent zirconium of mixed salt solution is 1～9;
The said cerium colloidal sol that contains is single compound colloidal sol or the colloidal sol that contains other rare earth element, described other rare earth element is meant that by period of element atom ordinal number be element in 57 to 71 the elementary composition group, and the molar ratio of other rare earth element in containing cerium colloidal sol is 0～0.60;
Said organic acid is selected from one or both in acetic acid, lauric acid, formic acid, the citric acid, and the organic acid molar weight is m a times of metal ion integral molar quantity in the mixed salt solution, and m preferred 1～5;
Said monomer is selected from vinylbenzene, vinyl acetate, vinylformic acid, methacrylic acid, methyl acrylate, the mix monomer of one or more in methyl methacrylate, butyl acrylate, butyl methacrylate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, divinyl and the kalimeris acid anhydrides etc., the volume ratio of said monomer and mixed salt solution is 1.2～2.5;
The initiator amount of selecting for use is the 0.5wt%～2wt% of monomer consumption;
Said tensio-active agent is selected from anionic, cationic, both sexes or non-ionic type, or low-molecular-weight or high-molecular weight tensio-active agent, and consumption is the 1wt%～10wt% of monomer consumption;
Step (2), 40 ℃～100 ℃ polyreactions, the reaction times is 2～24h with the emulsion of step (1), gel, with 80～200 ℃ of dryings of gel, 300～1000 ℃ of roastings 1～8 hour obtain said based on cerium oxide and zirconic composite oxide solid solution.
9. method according to claim 8, it is characterized in that, the said cerium colloidal sol that contains is the hydrochloric acid soln that contains the salpeter solution of cerous nitrate or contain cerous chlorate, wherein, cerous nitrate or the volumetric molar concentration that contains cerous chlorate are 0.1～2mol/l, said zirconium colloidal sol is the salpeter solution that contains zirconium nitrate, the salpeter solution of Zircosol ZN or the hydrochloric acid soln of basic zirconium chloride, and wherein, the volumetric molar concentration of zirconium nitrate, Zircosol ZN or basic zirconium chloride is 0.1～2mol/l.
10. method according to claim 8, it is characterized in that, initiator is selected from Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), ammonium persulphate, Potassium Persulphate, dibenzoyl peroxide, dilauroyl peroxide, isopropyl benzene hydroperoxide, peroxyesters or peroxy dicarbonates etc., and initiator amount is the 0.5wt%～2wt% of monomer consumption;
Said tensio-active agent is selected from anhydrous sorbitol oleic acid monoester such as commercially available Arlacel-80, sorbitan fatty acid ester Soxylat A 25-7 such as commercially available tween 20 and tween-80, octyl phenyl Soxylat A 25-7 such as the commercially available OP emulsifying agent and the segmented copolymer of triton x-100, polyvinylpyrrolidone, carboxymethyl cellulose, cetyl trimethylammonium bromide, sodium dodecyl benzenylsulfonate or oxyethane and propylene oxide.
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