CN101239309A - High specific area cerium aluminium base composite oxides and preparation thereof - Google Patents
High specific area cerium aluminium base composite oxides and preparation thereof Download PDFInfo
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Abstract
The present invention provides a cerium aluminum group composite oxide having a high specific surface area, wherein the chemical general equation is AlzCexRyO2, wherein R is one or more lanthanon, x, y, z are mol percentage of AL, Ce, R to sum of Al, Ce, R: x=10-50%, y=1-8%, z=1-x-y. The preparing method: a blended solution A of aluminum salt, cerium salt and R salt is prepared by the mol percentage constitute of the composite oxide; a precipitator solution B is prepared by chemical equivalentreaction calculation; an additive solution C is prepared by scaling additive according to quality theoretical value 5-20% of the cerium aluminum group composite oxide, the additive is a nonionics; a sediment suspension is prepared by mixing the solution A, C, adding solution B, controlling temperature and pH of the reaction system and evenly mixing; a cerium aluminum group composite oxide is obtained by separating, washing, drying and baking.
Description
One, technical field:
The present invention relates to a kind of high specific area cerium aluminium base composite oxides and preparation method thereof, this type of material can be widely used in all kinds of waste gas purifications or catalyst carrier material, eliminates and ceramic additive as motor vehicle tail-gas purifying, the out of stock desulfurization of flue gas, organic exhaust gas.
Two, technical background
Along with domestic and international emission regulation demands is further strict, more and more higher to the requirement of automotive emission.So far, installing ternary catalyzing unit additional is the important means of effectively controlling automotive emission.The composite oxide coating material of high-specific surface area has become critical material indispensable in the three-way catalyst as the cleaning catalyst for tail gases of automobiles auxiliary agent.Its effect mainly is the effective area that increases catalyst, improves the heat endurance of catalyst; Suitable microcellular structure and catalytic active center is provided; High degree of dispersion noble metal active component is saved noble metal dosage, reduces cost.
γ-Al in the coating material
2O
3, form the α phase easily undergoing phase transition more than 800 ℃, make micropore sinteredly, grain coarsening causes the specific area of coating to reduce, and catalytic activity descends.Studies show that in a large number, in slurry, add rare earth La, Ce and oxide stabilizer such as base metal Ba, Zr, Ca, can improve the temperature resistant capability of coating, stop crystal grain to be reunited, can improve the phase transition temperature of aluminum oxide coating layer.Simultaneously, because cerium oxide (CeO
2) have the chemical valence state changeability, by in oxidation or reducing atmosphere Ce takes place
4+Ce
3+Change, in oxygen-enriched atmosphere, store oxygen, in oxygen-lean atmosphere, discharge oxygen, can be used as hydrogen-storing material, the empty of three-way catalyst so played Chemical Regulation than window, thereby improve the redox reaction under oxygen deprivation and the oxygen enrichment state, make catalyst have excellent catalytic purification performance.
Present coating material research mainly concentrates on γ-Al
2O
3, cerium zirconium compound oxide or cerium zirconium sosoloid, relevant research patent is many, possesses different characteristics separately, but the specific area of Related product and high-temperature aging resisting performance all are not greatly improved.The active coating material that how to obtain high-specific surface area and high oxygen storage capacity becomes the focus of research, and its material also possesses the vast market using value.
The spy of Japan opens and has reported the mixed solution that uses cerous nitrate and zirconium nitrate among flat 6-279027 and the flat 8-16015 of Te Kai, obtains precipitated product thereby drip alkaline matter, product through 1000 ℃ of calcinings after specific area only be 15m
2/ g, specific area is dwindled seriously.
U.S. Pat 6,133,194, the preparation method of a kind of cerium zirconium compound oxide and cerium zirconium sosoloid is provided, by adding additive, has made the deposit seed even particle size distribution in the course of reaction, specific area increases, but product through 900 ℃ of roastings 6 hours aging after, specific area drops to 35m
2/ g, as seen the material high-temperature aging resisting performance of this method preparation is not high.
Reported among the Chinese patent CN1193948 that with zirconium nitrate and cerous nitrate be raw material, be higher than in temperature under 100 ℃ the condition, made cerium zirconates class precipitation, obtain combination product, but product specific area after 900 ℃ of roastings has been 30m by precipitating reagent
2/ g, product high-temperature aging resisting poor performance.
In the U.S. Pat 20020090512 the cerium Al based oxygen stored material of preparation molten through 5 hours metapores of 600 roastings be about 0.07ml/g, through 5 hours molten reducing to about 0.04ml/g of metapore of 800 calcinings, and production process working pressure tankage, equipment is huge, and production cost is higher.
In the United States Patent (USP) 20020049137 preparation cerium aluminium hydrogen-storing material through 800 roastings after 5 hours specific area have only 40m
2/ g, specific area is less.
Three, summary of the invention
The object of the invention provides a kind of high specific area cerium aluminium base composite oxides and preparation method thereof, and the present invention is more suitable in using in the middle of with three-way catalyst at motor vehicle tail-gas purifying, and it is simple to have production technology, the advantage of processing ease.
For reaching above-mentioned purpose, the present invention takes following technical scheme:
A kind of high specific area cerium aluminium base composite oxides of the present invention, its chemical general formula is: Al
zCe
xR
yO
2R is one or more rare earth element in the general formula, x, y, z be Al, Ce, R element respectively with the molar percentage of Al, Ce, R element sum: x=10～50%, y=1～8%, z=1-x-y, specific area is greater than 250m under the composite oxides fresh state that is obtained
2/ g, specific area is greater than 200m under the ageing state
2/ g.
The present invention has further taked following technical measures:
Measure one is: rare earth element is lanthanum, praseodymium, neodymium, yttrium or scandium.
Measure two is: fresh state refers to the powder of oxide behind calcination activation, and ageing state refers to: fresh attitude powder is through the powder of 900 ± 20 ℃ of high temperature ageings after 20 hours.
The preparation method of high specific area cerium aluminium base composite oxides of the present invention comprises following step:
Step 1) is formed according to the required molar percentage of composite oxides, the mixed solution A of preparation aluminium salt, cerium salt, R salt, the compound method of this mixed solution A is: form according to the molar percentage of Al, Ce, R and calculate, take by weighing aluminium salt, cerium salt and R salt respectively, with deionized water three kinds of salt being mixed with mass percent concentration respectively is 5%～40% salting liquid, at last above-mentioned three kinds of salting liquids all is mixed in together, stirs, be mixed solution A
Step 2) calculate preparation precipitant solution B according to the chemical reaction equivalent, this precipitating reagent B solution is the mixed solution of one or more alkaline matters and hydrogenperoxide steam generator, and the molal weight proportioning of alkaline matter and hydrogen peroxide is: 1: 1～2.5: 1,
Step 3) is according to 5～20% of the quality theoretical value that generates cerium aluminium base composite oxides, and taking by weighing additive and it is mixed with mass percent concentration is 10%～30% additive solution C, and this additive is a non-ionic surface active agent,
Step 4) mixes two kinds of solution of A, C according to 5: 1～20: 1 ratio of mass ratio after, then according to the solute mol ratio 1: 1.2～1: 1.5 of mixing in A, C solution and the B solution, described mixing A, C solution are added B solution, the temperature of reaction system is controlled in 7～11 the scope of being controlled in 40～60 ℃ the scope and with reacting system PH value, stir, generate precipitation suspension
Step 5) is isolated sediment from precipitation suspension, and sediment spends deionised water earlier, then with the ethanol washing,
The step 6) product is dried after filtration, roasting, the cerium aluminium base composite oxides of acquisition high-specific surface area.
The present invention has further taked following optimisation technique measure:
1. the described aluminum salt solution of step 1) is aluminium chloride, aluminum nitrate or aluminum sulfate solution, and the described cerium solution of step 1) is cerium chloride, cerous nitrate or cerous sulfate solution, and the described R salting liquid of step 1) is chloride, nitrate or sulfate liquor.
2. the described additive of step 3) is polyvinyl alcohol, POLYPROPYLENE GLYCOL, polyethylene glycol, alkylolamides etc.
3. step 2) described alkaline matter is ammoniacal liquor, carbon ammonium, urea, alkali-metal hydroxide, carbonate or acid carbonate.
4. the described washing of precipitate of step 5) is 2～4 times of precipitation quality with the amount of deionized water and ethanol, and washing times is 3～5 times.
5. common drying is adopted in the described oven dry of step 6), 90～120 ℃ of temperature controls, 6～15 hours time; Vacuum baking, 400～600 ℃ of calcination for activation temperature, roasting time 2～5 hours are adopted in roasting.
The salt of preparation reaction raw materials can be chloride, nitrate or sulfate in the above-mentioned reaction, is preferably nitrate, and its concentration range can be very wide, illustrates that it is limited little, and from the exercisable angle of reality, concentration generally is not less than 5wt%.
Above-mentioned reaction additive therefor is a non-ionic surface active agent, comprising: polyvinyl alcohol, POLYPROPYLENE GLYCOL, polyethylene glycol, alkylolamides or the like, the additive addition is preferably 10～15wt%.
The used precipitating reagent of above-mentioned reaction is the mixed solution of one or more alkaline matters and hydrogenperoxide steam generator, and wherein alkaline matter is: ammoniacal liquor, carbon ammonium, urea, alkali-metal hydroxide or carbonate or acid carbonate etc., preferred ammoniacal liquor.The mixed solution of ammoniacal liquor-hydrogen peroxide is pressed in the configuration of precipitating reagent, and the mol ratio of ammonia and hydrogen peroxide can be in 1.0～5.0 scopes.
Above-mentioned temperature of reaction system control range: 40～60 ℃, the reacting system PH value control range: 7～11, best PH=9～10.
Above-mentioned washing of precipitate is 2～4 times of precipitation quality with the amount of deionized water and ethanol, and washing times is 3～5 times.
Common drying is adopted in above-mentioned oven dry, 90～120 ℃ of temperature controls, 6～15 hours time; Vacuum baking, vacuum 0.2MPa, 400～600 ℃ of sintering temperatures, roasting time 2～5 hours are adopted in roasting.
According to above-mentioned condition, can obtain under the fresh state specific area greater than 250m
2/ g, specific area is 200m under the ageing state
2/ g, high specific area cerium aluminium base composite oxides.
Compared with prior art, the present invention has following advantage:
The present invention is more suitable for having the advantage that the cerium aluminium base composite oxides specific area is big, thermal stability is high, oxygen storage capacity is strong of preparation in using in the middle of with three-way catalyst at motor vehicle tail-gas purifying.
(1), adopt non-ionic surface active agent as: polyvinyl alcohol, POLYPROPYLENE GLYCOL, polyethylene glycol, alkylolamides or the like are as reaction additives, can play the effect of dispersion, emulsification, inhibition grain growth in the preparation process, in the roasting process of postorder, can remove, make the specific area of composite oxides improve a lot.
(2), self-control precipitant mix solution: the mixed solution of one or more alkaline matters and hydrogenperoxide steam generator, this mixed solution system is because the adding of hydrogen peroxide, make the alkalescence of precipitating reagent strengthen on the one hand, the hydrolysis of free hydroxyl and providing capability strengthen, help lend some impetus to precipitation reaction and finish rapidly, make tinyization of deposit seed; On the other hand because the decomposition of hydrogen peroxide in the course of reaction, make to produce with bubble in the reaction system that these bubbles can stop growing up of deposit seed to a certain extent, thereby increase the specific area of powder body material.The mixed solution of preferred ammoniacal liquor one hydrogen peroxide, the mol ratio of ammonia and hydrogen peroxide can be compared with other alkaline matter such as carbon ammonium or urea etc. when 1.0～5.0 scopes, and alkalescence is than the strongest, do not introduce other metallic element simultaneously in the precipitant mix solution, avoided the interference of exogenous impurity.Studies show that: this mixed precipitant has improved reaction speed, makes course of reaction effectively shorten, and deposit seed diminishes, and specific area increases.
(3), utilize ethanol washing, can effectively remove the hydrone in the sediment, stop hydrogen bond to form, prevent the dry hard aggregation that forms, make that powder granule is dispersed to be improved.Ethanol can make specific area improve to this property of deposit seed surface simultaneously, and heat endurance strengthens.
(4), production technology is simple, processing ease is suitable for realizing industrialization, gained powder body material specific area is big, and (specific area is greater than 250m under the fresh state
2/ g, specific area is greater than 200m under the ageing state
2/ g), thermal stability is good, and oxygen storage capacity is strong, and market application foreground is wide.
Four, description of drawings
Fig. 1 is embodiments of the invention sample and purchase sample fresh state specific area comparison diagram.
Fig. 2 is embodiments of the invention sample and purchase sample ageing state specific area comparison diagram.
Five, concrete embodiment
The invention will be further described below in conjunction with embodiment, but protection domain is not limited only to embodiment.
Embodiment 1:
This example explanation chemical general formula is Al
0.75Ce
0.2R
0.05O
2The preparation of cerium aluminium base composite oxides:
With 1.5mol Al (NO
3)
39H
2O, 0.4mol Ce (NO
3)
36H
2O, 0.1mol La (NO
3)
36H
2O and deionized water are made into 800ml mixed solution solution A, be heated to 45 ± 5 ℃, add additive (polyethylene glycol) 25g, stirred 10 minutes, adding by concentration then is the ammoniacal liquor of 5M and the hydrogen peroxide preparation 600ml precipitating reagent B solution of 4mol, pH value in the dropping process in the reaction system can increase gradually, constantly stir, treat that precipitating reagent all adds, 45 ± 5 ℃ of control temperature of reaction system, reaction system PH=9.0 ± 0.5, the adularescent precipitation generates, and continues stirred reaction mixture 30 minutes, with sedimentation and filtration, wash 3 times with deionized water and ethanol respectively, then sediment was placed 110 ± 10 ℃ of convection oven dry 10 hours, 500 ± 20 ℃ of vacuum kiln roastings 3 hours, vacuum degree control was 0.2MPa again, product is (fresh attitude) cerium aluminium base composite oxides, measures through the BET method: specific area is 321.98m
2/ g, the molten 0.78cm in hole
3/ g, aperture 97.59 ; Through 900 ± 20 ℃, high temperature ageing roasting in 20 hours is measured through the BET method: specific area 227.34m with fresh attitude oxide
2/ g, the molten 0.75cm in hole
3/ g, aperture 131.52 .
Embodiment 2
This example explanation chemical general formula is Al
0.6Ce
0.35R
0.05O
2The preparation of cerium aluminium base composite oxides:
With 1.2mol Al (NO
3)
39H
2O, 0.7mol Ce (NO
3)
36H
2O, 0.1mol La (NO
3)
36H
2O and deionized water are made into 600ml mixed solution solution A, be heated to 45 ± 5 ℃, add additive (polyethylene glycol) 20g, stirred 10 minutes, adding by concentration then is the ammoniacal liquor of 5M and the hydrogen peroxide preparation 400ml precipitating reagent B solution of 3mol, pH value in the dropping process in the reaction system can increase gradually, constantly stir, treat that precipitating reagent all adds, 50 ± 5 ℃ of control temperature of reaction system, reaction system PH=10.0 ± 0.5, the adularescent precipitation generates, and continues stirred reaction mixture 30 minutes, with sedimentation and filtration, wash 3 times with deionized water and ethanol respectively, then sediment was placed 110 ± 10 ℃ of convection oven dry 10 hours, again 600 ± 20 ℃ of vacuum kiln roastings 3 hours, vacuum 0.2MPa, product is (fresh attitude) cerium aluminium base composite oxides, measures through the BET method: specific area is 259.34m
2/ g, the molten 0.74cm in hole
3/ g, aperture 113.96 ; Through 900 ± 20 ℃, high temperature ageing roasting in 20 hours is measured through the BET method: specific area 214.32m with fresh attitude oxide
2/ g, the molten 0.73cm in hole
3/ g, aperture 136.90 .
Embodiment 3
This example explanation chemical general formula is Al
0.45Ce
0.5R
0.05O
2The preparation of cerium aluminium base composite oxides:
With 1.35mol Al (NO
3)
39H
2O, 1.5mol Ce (NO
3)
36H
2O, 0.15mol La (NO
3)
3 6H
20 with deionized water be made into 800ml mixed solution solution A, be heated to 45 ± 5 ℃, add additive (polyethylene glycol) 30g, stirred 10 minutes, adding by concentration then is the ammoniacal liquor of 5M and the hydrogen peroxide preparation 800ml precipitating reagent B solution of 5mol, pH value in the dropping process in the reaction system can increase gradually, constantly stir, treat that precipitating reagent all adds, 50 ± 5 ℃ of control temperature of reaction system, reaction system PH=10.0 ± 0.5, the adularescent precipitation generates, and continues stirred reaction mixture 30 minutes, with sedimentation and filtration, wash 3 times with deionized water and ethanol respectively, then sediment was placed 110 ± 10 ℃ of convection oven dry 10 hours, again 600 ± 20 ℃ of vacuum kiln roastings 3 hours, vacuum 0.2MPa, product is (fresh attitude) cerium aluminium base composite oxides, measures through the BET method: specific area is 326.64m
2/ g, the molten 0.78cm in hole
3/ g, aperture 95.61 ; Through 900 ± 20 ℃, high temperature ageing roasting in 20 hours is measured through the BET method: specific area 215.26m with fresh attitude oxide
2/ g, the molten 0.76cm in hole
3/ g, aperture 132.10 .
Under the fresh state: the comparing data of example and other each producer's samples
| The sample title | Sample state | BET specific area unit: m 2/g | Pore volume unit: cm 3/g | Average pore size unit: | Remarks |
| Embodiment 1 | Fresh | 321.9893 | 0.785586 | 97.5916 | |
| Embodiment 2 | Fresh | 259.3412 | 0.738839 | 113.9563 | |
| Embodiment 3 | Fresh | 326.6412 | 0.780798 | 95.6154 | |
| RH-25 | Fresh | 63.1116 | 0.209050 | 132.4955 | |
| CR-39 | Fresh | 161.8484 | 0.318847 | 78.8013 | |
| BK-10 | Fresh | 105.1101 | 0.318255 | 121.1128 |
Under the ageing state: the comparing data of example and other each producer's samples
| The sample title | Sample state | BET specific area unit: m 2/g | Pore volume unit: cm 3/g | Average pore size unit: | Remarks |
| Embodiment 1 | Aging | 227.3460 | 0.747506 | 131.5187 | 900±20℃，20h |
| Embodiment 2 | Aging | 214.3248 | 0.733539 | 136.9023 | |
| Embodiment 3 | Aging | 215.2643 | 0.762148 | 132.1045 | |
| RH-25 | Aging | 49.5225 | 0.198068 | 159.9822 | |
| CR-39 | Aging | 87.9212 | 0.328093 | 149.2668 | |
| BK-10 | Aging | 76.0926 | 0.298913 | 157.1311 |
Embodiment 4
A kind of high specific area cerium aluminium base composite oxides of the present invention, its chemical general formula is: Al
zCe
xR
yO
2R is one or more rare earth element in the general formula, x, y, z be Al, Ce, R element respectively with the molar percentage of Al, Ce, R element sum: x=10～50%, y=1～8%, z=1-x-y, for example: x=10%, y=1%, z=89%, x=50%, y=8%, z=42%, x=24%, y=3%, z=73%, perhaps, x=42%, y=5%, z=53%, specific area is greater than 250m2/g under the composite oxides fresh state that is obtained, and specific area is greater than 200m under the ageing state
2/ g.
Described rare earth element is lanthanum, praseodymium, neodymium, yttrium or scandium, in the present embodiment, described R can be chosen as the composition of lanthanum and praseodymium, its proportioning is any proportioning, it also can be the composition of praseodymium, neodymium and yttrium, its proportioning is any proportioning, and described R can also be any one rare earth element (as: lanthanum, praseodymium, neodymium, yttrium or a scandium etc.).
Described fresh state refers to the powder of oxide behind calcination activation, and ageing state refers to: fresh attitude powder is through the powder of 900 ± 20 ℃ of high temperature ageings after 20 hours.
Embodiment 5
The preparation method of high specific area cerium aluminium base composite oxides of the present invention comprises following step:
Step 1) is formed according to the required molar percentage of composite oxides, preparation aluminium salt, cerium salt, the mixed solution A of R salt, the compound method of this mixed solution A is: according to Al, Ce, the molar percentage of R is formed calculating, take by weighing aluminium salt respectively, cerium salt and R salt, with deionized water three kinds of salt being mixed with mass percent concentration respectively is 5%～40% salting liquid, in the present embodiment, it specifically can be formulated as mass percent concentration is 5%, 40% or 26% salting liquid, at last above-mentioned three kinds of salting liquids all are mixed in together, stir, be mixed solution A
Step 2) calculates preparation precipitant solution B according to the chemical reaction equivalent, this precipitating reagent B solution is the mixed solution of one or more alkaline matters and hydrogenperoxide steam generator, the molal weight proportioning of alkaline matter and hydrogen peroxide is: 1: 1～2.5: 1, present embodiment can be chosen as the molal weight proportioning of alkaline matter and hydrogen peroxide: 1: 1,2.5: 1 or 1.9: 1
Step 3) is according to 5～20% of the quality theoretical value that generates cerium aluminium base composite oxides, take by weighing additive, for example: take by weighing 5%, 13% or 20% of the quality theoretical value that generates cerium aluminium base composite oxides, and it is mixed with mass percent concentration is 10%～30% additive solution C, this additive is a non-ionic surface active agent, in the present embodiment, the mass percent concentration of additive solution C is 10%, 18% or 30%
Step 4) is with A, after two kinds of solution of C mix according to 5: 1～20: 1 ratio of mass ratio, then according to mixing A, solute mol ratio in C solution and the B solution 1: 1.2～1: 1.5, with described mixing A, C solution adds B solution, the temperature of reaction system is controlled in 7～11 the scope of being controlled in 40～60 ℃ the scope and with reacting system PH value, stir, generate precipitation suspension, in the present embodiment, A, two kinds of solution of C were according to mass ratio 5: 1, the ratio of 14: 1 or 20: 1 is mixed, above-mentioned mixing A, solute mol ratio in C solution and the B solution may be selected to be 1: 1.2,1: 1.3 or 1: 1.5, the control temperature of reaction system is 40,52 or 60 ℃, reacting system PH value can be 7 or 11, be preferably 9 or 10
Step 5) is isolated sediment from precipitation suspension, and sediment spends deionised water earlier, then with the ethanol washing,
The step 6) product is dried after filtration, roasting, the cerium aluminium base composite oxides of acquisition high-specific surface area.
The present invention has further taked following optimisation technique measure:
1. the described aluminum salt solution of step 1) is aluminium chloride, aluminum nitrate or aluminum sulfate solution, and the described cerium solution of step 1) is cerium chloride, cerous nitrate or cerous sulfate solution, and the described R salting liquid of step 1) is chloride, nitrate or sulfate liquor.
2. the described additive of step 3) is polyvinyl alcohol, POLYPROPYLENE GLYCOL, polyethylene glycol, alkylolamides etc.
3. step 2) described alkaline matter is ammoniacal liquor, carbon ammonium, urea, alkali-metal hydroxide, carbonate or acid carbonate.
4. the described washing of precipitate of step 5) is 2～4 times of precipitation quality with the amount of deionized water and ethanol, and washing times is 3～5 times.
5. common drying is adopted in the described oven dry of step 6), 90～120 ℃ of temperature controls, 6～15 hours time; Vacuum baking, 400～600 ℃ of calcination for activation temperature, roasting time 2～5 hours are adopted in roasting.
Claims (9)
1, a kind of high specific area cerium aluminium base composite oxides, its chemical general formula is: Al
zCe
xR
yO
2R is one or more rare earth element in the general formula, x, y, z be Al, Ce, R element respectively with the molar percentage of Al, Ce, R element sum: x=10～50%, y=1～8%, z=1-x-y, specific area is greater than 250m under the composite oxides fresh state that is obtained
2/ g, specific area is greater than 200m under the ageing state
2/ g.
2, high specific area cerium aluminium base composite oxides according to claim 1 is characterized in that rare earth element is lanthanum, praseodymium, neodymium, yttrium or scandium.
3, high specific area cerium aluminium base composite oxides according to claim 1 and 2 is characterized in that fresh state refers to the powder of oxide behind calcination activation, and ageing state refers to: fresh attitude powder is through the powder of 900 ± 20 ℃ of high temperature ageings after 20 hours.
4, the preparation method of the described high specific area cerium aluminium base composite oxides of a kind of claim 1 is characterized in that: comprise following step:
Step 1) is formed according to the required molar percentage of composite oxides, the mixed solution A of preparation aluminium salt, cerium salt, R salt, the compound method of this mixed solution A is: form according to the molar percentage of Al, Ce, R and calculate, take by weighing aluminium salt, cerium salt and R salt respectively, with deionized water three kinds of salt being mixed with mass percent concentration respectively is 5%～40% salting liquid, at last above-mentioned three kinds of salting liquids all is mixed in together, stirs, be mixed solution A
Step 2) calculate preparation precipitant solution B according to the chemical reaction equivalent, this precipitating reagent B solution is the mixed solution of one or more alkaline matters and hydrogenperoxide steam generator, and the molal weight proportioning of alkaline matter and hydrogen peroxide is: 1: 1～2.5: 1,
Step 3) is according to 5～20% of the quality theoretical value that generates cerium aluminium base composite oxides, and taking by weighing additive and it is mixed with mass percent concentration is 10%～30% additive solution C, and this additive is a non-ionic surface active agent,
Step 4) mixes two kinds of solution of A, C according to 5: 1～20: 1 ratio of mass ratio after, then according to the solute mol ratio 1: 1.2～1: 1.5 of mixing in A, C solution and the B solution, described mixing A, C solution are added B solution, the temperature of reaction system is controlled in 7～11 the scope of being controlled in 40～60 ℃ the scope and with reacting system PH value, stir, generate precipitation suspension
Step 5) is isolated sediment from precipitation suspension, and sediment spends deionised water earlier, then with the ethanol washing,
The step 6) product is dried after filtration, roasting, the cerium aluminium base composite oxides of acquisition high-specific surface area.
5, preparation method according to claim 4, it is characterized in that: the described aluminum salt solution of step 1) is aluminium chloride, aluminum nitrate or aluminum sulfate solution, the described cerium solution of step 1) is cerium chloride, cerous nitrate or cerous sulfate solution, and the described R salting liquid of step 1) is chloride, nitrate or sulfate liquor.
6, preparation method according to claim 4 is characterized in that additive is polyvinyl alcohol, POLYPROPYLENE GLYCOL, polyethylene glycol, alkylolamides.
7, preparation method according to claim 4 is characterized in that step 2) described alkaline matter is ammoniacal liquor, carbon ammonium, urea, alkali-metal hydroxide, carbonate or acid carbonate.
8, preparation method according to claim 4 is characterized in that the described washing of precipitate of step 5) is 2～4 times of precipitation quality with the amount of deionized water and ethanol, and washing times is 3～5 times.
9, preparation method according to claim 4 is characterized in that the described oven dry of step 6) adopts common drying, 90～120 ℃ of temperature controls, 6～15 hours time; Vacuum baking, 400～600 ℃ of calcination for activation temperature, roasting time 2～5 hours are adopted in roasting.
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