CN102824904A - Composite aluminium, cerium and zirconium oxide catalytic material and method for producing same - Google Patents
Composite aluminium, cerium and zirconium oxide catalytic material and method for producing same Download PDFInfo
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Abstract
The invention aims to disclose a composite aluminium, cerium and zirconium oxide catalytic material and a method for producing the same. The composite aluminium, cerium and zirconium oxide catalytic material is a composite oxide which consists of 15-30% of cerium oxide, 5-20% of zirconium oxide, 50-75% of aluminium oxide and 0-5% of other rear earth oxides expect cerium by weight. Compared with the prior art, the aluminium oxide is subjected to surface treatment, on one hand, the interaction of the aluminium oxide and the cerium and zirconium-base composite oxides is enhanced; and on the other hand, the uniformity of the aluminium oxide and the cerium and zirconium-base composite oxides is fully ensured; through the modification of a structural directing agent and a dispersing agent, the pore diameter and pore volume of the composite aluminium, cerium and zirconium oxide catalytic material are further improved, and good temperature resistance and aging resistance are obtained; and moreover, the composite aluminium, cerium and zirconium oxide catalytic material has the advantages of high oxygen storage capability and high oxygen storage and release velocities, so the purpose of the invention is realized.
Description
Technical field
The present invention relates to a kind of catalysis material and preparation method thereof, particularly a kind ofly be applicable to that purifying vehicle exhaust, organic exhaust gas are eliminated and the aluminium cerium zirconium compound oxide catalysis material of waste gas purification such as natural gas catalytic combustion or catalytic combustion and preparation method thereof.
Background technology
Reducing automobile exhaust pollution, protect atmosphere quality, realize the sustainable development of ecological environment and society, is one of important topic that reaches at present China environmental protection in the following long duration.
Pollute for reducing, must break through from improving gasoline quality, improve the engine combustion state and increasing exhaust purification catalytic efficient three aspects.Up to the present, using cleaning catalyst for tail gases of automobiles is that effective way reduces HC in the tail gas, CO and NO through three-way catalytic apparatus exactly
xThe content of three kinds of toxic gases.
Three-way catalyst mainly is by the noble metal active component that plays catalytic action, contains CeO
2Catalyst aid (hydrogen-storing material) and being used to supports the carrier of active component and forms.And suitable purifying vehicle exhaust storage oxygen coating material is to the dispersion and stable the playing a key effect of noble metal; Store up the oxygen storage capacity that the oxygen coating material can improve catalyst under the hot conditions simultaneously; Enlarge its air-fuel ratio operation window, catalyst activity under very harsh operating condition is had clear improvement.
The rare earth hydrogen-storing material that contains cerium of present commercial usefulness and γ-Al with high-specific surface area and strong thermal ageing resistant capacity
2O
3Prepare respectively.
Because CeO
2Heat endurance relatively poor, limited its use.Must suppress CeO when therefore, at high temperature using
2Sintering.When with CeO
2In cerium ion when replacing with other cationic moiety, can produce fault of construction, obviously improve its high high-temp stability.
Zr0
2Add Ce0 to
2In, can form Ce0
2-Zr0
2Solid solution and improve Ce0
2The body phase behaviour, be beneficial to the migration and the diffusion of body phase oxygen atom, body phase reaction process is become vivaciously, can improve Ce0
2Oxygen storage capacity and high-temperature stability.Simultaneously, the adding of rare earth such as Pr, Nd, Y, Nb, La and Ba and alkaline earth element can further strengthen the high-temperature aging resisting property of hydrogen-storing material, improves its oxygen storage capacity.Hydrogen-storing material is the dispersion of stabilizing active component effectively; Therefore have big specific area, bigger pore volume and suitable pore-size distribution, and the cerium zirconium based oxygen storage material with good high-temperature aging resisting performance, excellent low-temperature catalyzed performance becomes the critical material of new three-way catalyst.
γ-Al
2O
3Heat endurance, specific area, pore volume, pore-size distribution, surface acidity and NO adsorption capacity influence the catalytic performance of catalyst to a great extent.Improve γ-Al
2O
3High high-temp stability and surface property significant to improving activity of such catalysts and service life.Research shows.Through adding the high high-temp stability that rare earth, alkaline earth element etc. can improve aluminium oxide, suppress aluminium oxide by the γ transformation of α phase in opposite directions.At present widely used in the industry is boehmite to be carried out surface modification after the roasting preparation has the aluminium oxide of strong thermal ageing resistant capacity through rare earth element or transition metal.
With rare earth material and the mutual modifications of aluminium oxide such as cerium zirconium based solid solutions; Prepare Ce-Zr-Al based composite; Making its common advantage that has hydrogen-storing material and aluminium oxide concurrently, improve the high temperature ageing resistance of hydrogen-storing material and aluminium oxide, is the key technology of catalyst coatings of new generation.
The Chinese patent patent No. is that 200510020615.1 patent of invention discloses a kind of Ce-Zr-Al based oxygen stored material and preparation method thereof; Its basic composition is by cerium oxide, zirconia, aluminium oxide and stabilizing agent, and stabilizing agent is selected from least a of lanthana, yittrium oxide and alkaline earth oxide; Its preparation technology is that (1) prepares nitrate mixed solution and alkaline precipitating agent by given material composition component; The two kinds of solution and the conductance that (2) will prepare go in the reaction vessel to precipitate, and deposition finishes the back and is not less than 2h 90-100 ℃ of ageing; (3) the reaction feed liquid after the ageing is carried out Separation of Solid and Liquid, and isolated solid phase precipitation thing washs, is made into slurries with surfactant and water then; (4) slurries are through evaporation drying, roasting gets Ce-Zr-Al based oxygen stored material then.
Specific surface agent with the hydrogen-storing material of method for preparing reaches as high as 110m behind 1000 ℃ of roasting 5h
2More than/the g, can reach 38m at least
2More than/the g; But this method is a raw material with the aluminum nitrate, and cost is higher, and the hydrogen-storing material aperture of preparing simultaneously is less, the high temperature ageing resistace of hydrogen-storing material is relatively poor.
The Chinese patent patent publication No. is that the patent of invention of CN101940921A discloses a kind of double-decker hydrogen-storing material and preparation method thereof, by cerium zirconium sosoloid and Large ratio surface γ-Al
2O
3Be composited, its preparation method is: lanthanum nitrate hexahydrate, cerous nitrate solution, yttrium nitrate and zirconium nitrate solution are got in (1), insert to add ammoniacal liquor in the container and precipitate and obtain sediment; (2) the industrial hydrogen peroxide solution of adding cerium oxide quality in the sediment of step (1) obtains cerium zirconium precursor compound; (3) with presoma and γ-Al
2O
3Mass ratio 1:1 mixes, stirring obtains mixture; (4) with the mixture in the step (3) through washing, filter, add surfactant after, pulverize through oven dry, roasting, air-flow again, double-deck powder hydrogen-storing material.
Said method is with cerium zirconium precursor body and γ-Al
2O
3Mechanical mixture, this has just caused the caking property of mixing uniformity and aluminium oxide and cerium zirconium compound oxide of aluminium oxide and cerium zirconium compound oxide relatively poor, influences the catalytic performance and the high-temperature thermal stability agent of hydrogen-storing material.
The Chinese patent patent No. is that 98108256.4 patent of invention discloses a kind of method that has the hydrogen-storing material of high thermal stability and prepare this material; On the specific surface of high surface area carriers such as aluminium oxide, zirconia, titanium oxide, silica or other oxides, and then get cerium oxide and at least a stabilizing agent high degree of dispersion that is selected from praseodymium oxide, lanthana, yittrium oxide and neodymia through roasting; Its preparation method be the precursor and the cerium oxide of described stabilizing agent of dissolving be added to a kind of preprepared, in the water dispersion of the selected carrier mass that constantly stirring; Then through adding alkali; The pH value that slowly improves disperse object is to 8-10, thereby stabilizing agent and cerium oxide are deposited on the carrier mass.
Said method does not carry out surface treatment to carrier, and granular size of carrier, pattern etc. all affect the cohesive force of cladding uniformity and coat and carrier, influences the catalytic activity and the high high-temp stability of hydrogen-storing material.
To sum up, existing less for the research of Ce-Zr-Al based rare earth hydrogen-storing material, and the adhesion between cerium zirconium and the aluminium oxide and high temperature ageing resistance exist bigger contradiction, and the high temperature ageing resistance of material is relatively poor.
Therefore, need a kind of aluminium cerium zirconium compound oxide catalysis material and preparation method thereof especially, to solve the above-mentioned existing problem that exists.
Summary of the invention
The object of the present invention is to provide a kind of aluminium cerium zirconium compound oxide catalysis material and preparation method thereof; Deficiency to prior art; Have that specific area is big, the high temperature ageing resistance is good and store characteristics such as oxygen ability height, be applicable to waste gas purification or catalytic combustions such as purifying vehicle exhaust, organic exhaust gas elimination and natural gas catalytic combustion.
The technical problem that the present invention solved can adopt following technical scheme to realize:
On the one hand, the present invention provides a kind of aluminium cerium zirconium compound oxide catalysis material, it is characterized in that, it is by the composite oxides that cerium oxide, zirconia, aluminium oxide and other rare earth oxides except that cerium are formed, and its percentage by weight is following:
Cerium oxide: 15-30%;
Zirconia: 5-20%;
Aluminium oxide: 50-75%;
Other rare earth oxides: 0-5% except that cerium.
In one embodiment of the invention, said other rare earth oxides except that cerium are selected from one or more the combination in lanthana, yittrium oxide, praseodymium oxide and the neodymia.
On the other hand, the present invention provides a kind of preparation method of aluminium cerium zirconium compound oxide catalysis material, it is characterized in that it comprises the steps:
(1) preparation of active component slurries: according to the composition of material that corresponding cerous nitrate, other rare earth soluble-salts and zirconium nitrate except that cerium is water-soluble, the hybrid metal nitrate solution; In the hybrid metal nitrate solution, add activated alumina and structure directing agent, shear and disperse, get active component slurries A;
(2) deposition: at a certain temperature, ammoniacal liquor is added among the above-mentioned active component slurries A,, add Ce up to the deposition terminal point
3+Be oxidized to Ce
4+Required stoichiometric hydrogen peroxide solution, the insulation certain hour gets sediment B;
(3) sedimentary surface treatment is dewatered sediment B, wash; Sediment B and water after the dehydration with mass ratio 2:1 reslurry, are added a certain amount of surface conditioning agent, shear dispersion;
(4) roasting at 550-750 ℃ of following roasting 4-6h, gets said cerium aluminium cerium zirconium compound oxide catalysis material with surface treated sediment B.
In one embodiment of the invention; In the step (1); Said other rare earth solubility nitrate except that cerium are selected from the one or more combination in lanthanum nitrate, yttrium nitrate, praseodymium nitrate, the neodymium nitrate, and perhaps nitric acid and lanthana, yittrium oxide, praseodymium oxide and neodymia reaction generate corresponding nitrate solution.
In one embodiment of the invention, in the step (1), in the said mixed metal salt salpeter solution, the ratio of each nitrate is:
Cerous nitrate 15-30%;
Zirconium nitrate 5-20%;
Other rare earth solubility nitrate 0-5% except that cerium.
In one embodiment of the invention, in the step (1), the addition of activated alumina is the 25%-35% that activated alumina accounts for activated alumina and each metal nitrate summation in the said active component slurries.
In one embodiment of the invention, in the step (1), said activated alumina is selected from gama-alumina that pore volume is 0.3-0.7g/ml or is the gama-alumina that the boehmite of 0.3-0.7g/ml obtains behind 3-6h after the 450-600 ℃ of roasting with pore volume.
In one embodiment of the invention, in the step (1), said structure directing agent is selected from organic ammonium salt, and the addition of said structure directing agent is the 15-30% of the quality summation of each nitrate in mixing.
Further, said structure directing agent is preferably one or both the combination in ammonium citrate and the softex kw.
In one embodiment of the invention, in the step (2), said ageing temperature is 60-90 ℃, and digestion time is 1-4h.
Further, preferably, said ageing temperature is 80-90 ℃, and said digestion time is 2-3h.
In one embodiment of the invention, in the step (3), said surface conditioning agent is selected from aliphatic acid or the ethers that carbon atom is 6-12, and the addition of said surface conditioning agent is the 30-50% of the weight summation of each nitrate.
Further, said carbon atom is that aliphatic acid or the ethers of 6-12 comprises sad (C
8H
16O
2), capric acid (C
10H
20
2), ethylene glycol monobutyl ether (C
6H
14O
2) and diethylene glycol monobutyl ether (C
8H
18O
3).
Aluminium cerium zirconium compound oxide catalysis material of the present invention and preparation method thereof, compared with prior art, through aluminium oxide is carried out surface treatment, the interaction between oxidation reinforced aluminium and the Ce-Zr based composite oxide on the one hand; Guarantee the homogeneity between aluminium oxide and the Ce-Zr based composite oxide on the other hand fully; Through the modification of structure directing agent and dispersant, further improved the aperture and the pore volume of product, have good high-temperature aging resisting ability, have the oxygen storage capacity height simultaneously and store the fireballing advantage of oxygen, realize the object of the invention.
Characteristics of the present invention can consult this case graphic and below better embodiment detailed description and obtain to be well understood to.
Description of drawings
Fig. 1 is the XRD sketch map of embodiments of the invention 1 preparation aluminium cerium zirconium compound oxide catalysis material.
The specific embodiment
For technological means, creation characteristic that the present invention is realized, reach purpose and effect and be easy to understand and understand, below in conjunction with concrete diagram, further set forth the present invention.
Aluminium cerium zirconium compound oxide catalysis material of the present invention and preparation method thereof, it is by the composite oxides that cerium oxide, zirconia, aluminium oxide and other rare earth oxides except that cerium are formed, and its percentage by weight is following:
Cerium oxide: 15-30%;
Zirconia: 5-20%;
Aluminium oxide: 50-75%;
Other rare earth oxides: 0-5% except that cerium.
In the present invention, said other rare earth oxides except that cerium are selected from one or more the combination in lanthana, yittrium oxide, praseodymium oxide and the neodymia.
The preparation method of aluminium cerium zirconium compound oxide catalysis material of the present invention, it comprises the steps:
(1) preparation of active component slurries: according to the composition of material that corresponding cerous nitrate, other rare earth soluble-salts and zirconium nitrate except that cerium is water-soluble, the hybrid metal nitrate solution; In the hybrid metal nitrate solution, add activated alumina and structure directing agent, shear and disperse, get active component slurries A;
(2) deposition: at a certain temperature, ammoniacal liquor is added among the above-mentioned active component slurries A,, add Ce up to the deposition terminal point
3+Be oxidized to Ce
4+Required stoichiometric hydrogen peroxide solution, the insulation certain hour gets sediment B;
(3) sedimentary surface treatment is dewatered sediment B, wash; Sediment B and water after the dehydration with mass ratio 2:1 reslurry, are added a certain amount of surface conditioning agent, shear dispersion;
(4) roasting at 550-750 ℃ of following roasting 4-6h, gets said cerium aluminium cerium zirconium compound oxide catalysis material with surface treated sediment B.
In step (1); Said other rare earth solubility nitrate except that cerium are selected from the one or more combination in lanthanum nitrate, yttrium nitrate, praseodymium nitrate, the neodymium nitrate, and perhaps nitric acid and lanthana, yittrium oxide, praseodymium oxide and neodymia reaction generate corresponding nitrate solution.
In the said mixed metal salt salpeter solution, the ratio of each nitrate is:
Cerous nitrate 15-30%;
Zirconium nitrate 5-20%;
Other rare earth solubility nitrate 0-5% except that cerium.
The addition of activated alumina is the 25%-35% that activated alumina accounts for activated alumina and each metal nitrate summation in the said active component slurries.
Said activated alumina is selected from gama-alumina that pore volume is 0.3-0.7g/ml or is the gama-alumina that the boehmite of 0.3-0.7g/ml obtains behind 3-6h after the 450-600 ℃ of roasting with pore volume.
Said structure directing agent is selected from organic ammonium salt, and the addition of said structure directing agent is the 15-30% of the quality summation of each nitrate in mixing; Said structure directing agent is preferably one or both the combination in ammonium citrate and the softex kw.
In step (2), said ageing temperature is 60-90 ℃, and digestion time is 1-4h; Preferably, said ageing temperature is 80-90 ℃, and said digestion time is 2-3h.
In step (3), said surface conditioning agent is selected from aliphatic acid or the ethers that carbon atom is 6-12, and the addition of said surface conditioning agent is the 30-50% of the weight summation of each nitrate; Said carbon atom is that aliphatic acid or the ethers of 6-12 comprises sad (C
8H
16O
2), capric acid (C
10H
20
2), ethylene glycol monobutyl ether (C
6H
14O
2) and diethylene glycol monobutyl ether (C
8H
18O
3).
Embodiment 1
With the dissolving of 500kg pure water, adding the 60kg pore volume is γ-Al of 0.31g/ml with 64.9kg cerous nitrate, 29.8kg zirconium nitrate, 13.5kg lanthanum nitrate
2O
3, the 16kg ammonium citrate, shear to disperse; After above-mentioned slurries are heated to 60 ℃, slowly add ammoniacal liquor, the pH of control terminal point is 9, adds 30% hydrogen peroxide solution 11.8kg, insulation 4h.After the sediment centrifugal dehydration, mix according to mass ratio 2:1, add diethylene glycol monobutyl ether (C8H18O3) 32.5kg, shear and disperse with water.Turbid liquid after disperseing through 550 ℃ of roasting 6h, is got said aluminium cerium zirconium compound oxide catalysis material.
Consisting of of this material, cerium oxide 24%, zirconia 11%, lanthana 5%, aluminium oxide 60%.The fresh specific area of this material is 140m
2/ g, the specific area that this material is obtained behind 1000 ℃ of roasting 4h is 101m
2/ g.
Embodiment 2
With the dissolving of 500kg pure water, adding the 60kg pore volume is γ-Al of 0.68g/ml with 64.9kg cerous nitrate, 29.8kg zirconium nitrate, 13.5kg lanthanum nitrate
2O
3, the 16kg ammonium citrate, shear to disperse; After above-mentioned slurries are heated to 60 ℃, slowly add ammoniacal liquor, the pH of control terminal point is 9, adds 30% hydrogen peroxide solution 11.8kg, insulation 1h.After the sediment centrifugal dehydration, mix according to mass ratio 2:1, add ethylene glycol monobutyl ether (C6H14O2) 54.1kg, shear and disperse with water.Turbid liquid after disperseing through 750 ℃ of roasting 4h, is got said aluminium cerium zirconium compound oxide catalysis material.
Consisting of of this material, cerium oxide 24%, zirconia 11%, lanthana 5%, aluminium oxide 60%.The fresh specific area of this material is 182m
2/ g, the specific area that this material is obtained behind 1000 ℃ of roasting 4h is 132m
2/ g.
Embodiment 3
64.9kg cerous nitrate, 29.8kg zirconium nitrate, 13.5kg lanthanum nitrate are dissolved with the 500kg pure water.With pore volume be the boehmite of 0.35g/ml behind 6h after 450 ℃ of roastings γ-Al
2O
3, get 60kg γ-Al
2O
3Join in the above-mentioned solution, the 32.46kg softex kw is sheared and is disperseed; After above-mentioned slurries are heated to 60 ℃, slowly add ammoniacal liquor, the pH of control terminal point is 9, adds 30% hydrogen peroxide solution 11.8kg, insulation 1h.After the sediment centrifugal dehydration, mix according to mass ratio 2:1, add ethylene glycol monobutyl ether (C6H14O2) 54.1kg, shear and disperse with water.Turbid liquid after disperseing through 600 ℃ of roasting 4h, is got said aluminium cerium zirconium compound oxide catalysis material.
Consisting of of this material, cerium oxide 24%, zirconia 11%, lanthana 5%, aluminium oxide 60%.The fresh specific area of this material is 193m
2/ g, the specific area that this material is obtained behind 1000 ℃ of roasting 4h is 145m
2/ g.
Embodiment 4
With the dissolving of 500kg pure water, adding the 75kg pore volume is γ-Al of 0.68g/ml with 40.5kg cerous nitrate, 13.5kg zirconium nitrate
2O
3, the 25kg ammonium citrate, shear to disperse; After above-mentioned slurries are heated to 90 ℃, slowly add ammoniacal liquor, the pH of control terminal point is 9, adds 30% hydrogen peroxide solution 11.8kg, insulation 1h.After the sediment centrifugal dehydration, mix according to mass ratio 2:1, add sad (C8H16O2) 30kg, shear and disperse with water.Turbid liquid after disperseing through 60 ℃ of roasting 4h, is got said aluminium cerium zirconium compound oxide catalysis material.
Consisting of of this material, cerium oxide 15%, zirconia 5%, aluminium oxide 75%.The fresh specific area of this material is 195m
2/ g, the specific area that this material is obtained behind 1000 ℃ of roasting 4h is 151m
2/ g.
Embodiment 5
With the dissolving of 500kg pure water, adding the 50kg pore volume is γ-Al of 0.51g/ml with 81kg cerous nitrate, 52.6kg zirconium nitrate
2O
3, the 25kg ammonium citrate, shear to disperse; After above-mentioned slurries are heated to 90 ℃, slowly add ammoniacal liquor, the pH of control terminal point is 9, adds 30% hydrogen peroxide solution 11.8kg, insulation 1h.After the sediment centrifugal dehydration, mix according to mass ratio 2:1, add capric acid (C10H202) 30kg, shear and disperse with water.Turbid liquid after disperseing through 60 ℃ of roasting 4h, is got said aluminium cerium zirconium compound oxide catalysis material.
Consisting of of this material, cerium oxide 30%, zirconia 20%, aluminium oxide 50%.The fresh specific area of this material is 172m
2/ g, the specific area that this material is obtained behind 1000 ℃ of roasting 4h is 144m
2/ g.
Embodiment 6
With 54kg cerous nitrate, 26.3kg zirconium nitrate, 2.7kg yttrium nitrate, the 1.5kg praseodymium nitrate, the 4.5kg neodymium nitrate dissolves with the 500kg pure water.With the 67kg pore volume is 0.4g/ml 60kg γ-Al
2O
3Join in the above-mentioned solution, the 32.46kg softex kw is sheared and is disperseed; After above-mentioned slurries are heated to 80 ℃, slowly add ammoniacal liquor, the pH of control terminal point is 9, adds 30% hydrogen peroxide solution 9.5kg, insulation 2h.After the sediment centrifugal dehydration, mix according to mass ratio 2:1, add ethylene glycol monobutyl ether (C6H14O2) 54.1kg, shear and disperse with water.Turbid liquid after disperseing through 600 ℃ of roasting 4h, is got said aluminium cerium zirconium compound oxide catalysis material.
Consisting of of this material, cerium oxide 20%, zirconia 10%, yittrium oxide 1%, praseodymium oxide 0.5%, neodymia 1.5%, aluminium oxide 67%.The fresh specific area of this material is 193m
2/ g, the specific area that this material is obtained behind 1000 ℃ of roasting 4h is 145m
2/ g.
More than show and described basic principle of the present invention and principal character and advantage of the present invention.The technical staff of the industry should understand; The present invention is not restricted to the described embodiments; That describes in the foregoing description and the specification just explains principle of the present invention, and under the prerequisite that does not break away from spirit and scope of the invention, the present invention also has various changes and modifications; These variations and improvement all fall in the scope of the invention that requires protection, and the present invention requires protection domain to be defined by appending claims and equivalent thereof.
Claims (13)
1. aluminium cerium zirconium compound oxide catalysis material and preparation method thereof is characterized in that, it is by the composite oxides that cerium oxide, zirconia, aluminium oxide and other rare earth oxides except that cerium are formed, and its percentage by weight is following:
Cerium oxide: 15-30%;
Zirconia: 5-20%;
Aluminium oxide: 50-75%;
Other rare earth oxides: 0-5% except that cerium.
2. aluminium cerium zirconium compound oxide catalysis material as claimed in claim 1 is characterized in that, said other rare earth oxides except that cerium are selected from one or more the combination in lanthana, yittrium oxide, praseodymium oxide and the neodymia.
3. the preparation method of an aluminium cerium zirconium compound oxide catalysis material is characterized in that it comprises the steps:
(1) preparation of active component slurries: according to the composition of material that corresponding cerous nitrate, other rare earth soluble-salts and zirconium nitrate except that cerium is water-soluble, the hybrid metal nitrate solution; In the hybrid metal nitrate solution, add activated alumina and structure directing agent, shear and disperse, get active component slurries A;
(2) deposition: at a certain temperature, ammoniacal liquor is added among the above-mentioned active component slurries A,, add Ce up to the deposition terminal point
3+Be oxidized to Ce
4+Required stoichiometric hydrogen peroxide solution, the insulation certain hour gets sediment B;
(3) sedimentary surface treatment is dewatered sediment B, wash; Sediment B and water after the dehydration with mass ratio 2:1 reslurry, are added a certain amount of surface conditioning agent, shear dispersion;
(4) roasting at 550-750 ℃ of following roasting 4-6h, gets said cerium aluminium cerium zirconium compound oxide catalysis material with surface treated sediment B.
4. the preparation method of aluminium cerium zirconium compound oxide catalysis material as claimed in claim 3; It is characterized in that; In the step (1); Said other rare earth solubility nitrate except that cerium are selected from the one or more combination in lanthanum nitrate, yttrium nitrate, praseodymium nitrate, the neodymium nitrate, and perhaps nitric acid and lanthana, yittrium oxide, praseodymium oxide and neodymia reaction generate corresponding nitrate solution.
5. the preparation method of aluminium cerium zirconium compound oxide catalysis material as claimed in claim 3 is characterized in that, in the step (1), in the said mixed metal salt salpeter solution, the ratio of each nitrate is:
Cerous nitrate 15-30%;
Zirconium nitrate 5-20%;
Other rare earth solubility nitrate 0-5% except that cerium.
6. the preparation method of aluminium cerium zirconium compound oxide catalysis material as claimed in claim 3; It is characterized in that; In the step (1), the addition of activated alumina is the 25%-35% that activated alumina accounts for activated alumina and each metal nitrate summation in the said active component slurries.
7. the preparation method of aluminium cerium zirconium compound oxide catalysis material as claimed in claim 3; It is characterized in that; In the step (1), said activated alumina is selected from gama-alumina that pore volume is 0.3-0.7g/ml or is the gama-alumina that the boehmite of 0.3-0.7g/ml obtains behind 3-6h after the 450-600 ℃ of roasting with pore volume.
8. the preparation method of aluminium cerium zirconium compound oxide catalysis material as claimed in claim 3; It is characterized in that; In the step (1), said structure directing agent is selected from organic ammonium salt, and the addition of said structure directing agent is the 15-30% of the quality summation of each nitrate in mixing.
9. the preparation method of aluminium cerium zirconium compound oxide catalysis material as claimed in claim 8 is characterized in that, said structure directing agent is preferably one or both the combination in ammonium citrate and the softex kw.
10. the preparation method of aluminium cerium zirconium compound oxide catalysis material as claimed in claim 3 is characterized in that, in the step (2), said ageing temperature is 60-90 ℃, and digestion time is 1-4h.
11. the preparation method of aluminium cerium zirconium compound oxide catalysis material as claimed in claim 10 is characterized in that, preferably, said ageing temperature is 80-90 ℃, and said digestion time is 2-3h.
12. the preparation method of aluminium cerium zirconium compound oxide catalysis material as claimed in claim 3; It is characterized in that; In the step (3), said surface conditioning agent is selected from aliphatic acid or the ethers that carbon atom is 6-12, and the addition of said surface conditioning agent is the 30-50% of the weight summation of each nitrate.
13. the preparation method of aluminium cerium zirconium compound oxide catalysis material as claimed in claim 12 is characterized in that, said carbon atom is that aliphatic acid or the ethers of 6-12 comprises sad (C
8H
16O
2), capric acid (C
10H
20
2), ethylene glycol monobutyl ether (C
6H
14O
2) and diethylene glycol monobutyl ether (C
8H
18O
3).
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN102962047B (en) * | 2012-11-12 | 2014-10-08 | 上海华明高纳稀土新材料有限公司 | Aluminum-cerium-zirconium based composite oxide catalytic material and preparation method thereof |
| CN102962047A (en) * | 2012-11-12 | 2013-03-13 | 上海华明高纳稀土新材料有限公司 | Aluminum-cerium-zirconium based composite oxide catalytic material and preparation method thereof |
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| CN108136374A (en) * | 2015-10-27 | 2018-06-08 | 株式会社科特拉 | Exhaust gas purification catalyst and its manufacturing method and use its waste gas purification apparatus |
| US10828602B2 (en) | 2015-10-27 | 2020-11-10 | Cataler Corporation | Exhaust gas purifying catalyst and method for producing same, and exhaust gas purification device using same |
| CN108136374B (en) * | 2015-10-27 | 2021-06-22 | 株式会社科特拉 | Exhaust gas purifying catalyst, method for producing same, and exhaust gas purifying apparatus using same |
| CN110366445A (en) * | 2016-12-23 | 2019-10-22 | 罗地亚经营管理公司 | The anti-aging mixed oxide made of cerium, zirconium, aluminium and lanthanum for motor vehicles catalytic converter |
| CN108212140A (en) * | 2017-12-13 | 2018-06-29 | 昆明贵研催化剂有限责任公司 | The high oxygen storage capacity Al of automotive catalyst2O3-CeO2-ZrO2-TiO2Coating material and preparation method thereof |
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| CN109225213A (en) * | 2018-10-08 | 2019-01-18 | 江苏几维环境科技有限公司 | A kind of preparation method of motor vehicle tail-gas purifying close coupling three-way catalyst |
| CN109529802A (en) * | 2018-11-12 | 2019-03-29 | 山东国瓷功能材料股份有限公司 | A kind of cerium zirconium compound oxide and its preparation method and application |
| CN109529802B (en) * | 2018-11-12 | 2021-12-28 | 山东国瓷功能材料股份有限公司 | Cerium-zirconium composite oxide and preparation method and application thereof |
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