CN104437458B - Cerium-zirconium-based composite oxide catalytic material and preparation method thereof - Google Patents
Cerium-zirconium-based composite oxide catalytic material and preparation method thereof Download PDFInfo
- Publication number
- CN104437458B CN104437458B CN201410634981.5A CN201410634981A CN104437458B CN 104437458 B CN104437458 B CN 104437458B CN 201410634981 A CN201410634981 A CN 201410634981A CN 104437458 B CN104437458 B CN 104437458B
- Authority
- CN
- China
- Prior art keywords
- cerium
- rare earth
- solid solution
- zirconium
- oxygen storage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a cerium-zirconium-based composite oxide catalytic material and a preparation method thereof. The cerium-zirconium-based composite oxide catalytic material is characterized by comprising a cerium-zirconium-based solid solution rare earth oxygen-storage material, kaolin and aluminum oxide. Compared with the prior art, the cerium-zirconium-based composite oxide catalytic material has the characteristics of large specific surface area, good high-temperature aging resistance, high oxygen storage and discharge capability, and the like, and meanwhile, has the excellent mechanical strength, such as pressure resistance and abrasion resistance; the cerium-zirconium-based composite oxide catalytic material is suitable for treating industrial waste gas, purifying human settlement, treating waste gas of the petrochemical industry, and the like.
Description
Technical field
The present invention relates to a kind of catalysis material and preparation method thereof, more particularly to it is a kind of be applied to motor vehicle tail-gas purifying,
The Ce-Zr based composite oxide catalysis material of the exhaust-gas treatments such as industrial waste gas, human settlement's purification and petrochemical industry and its preparation side
Method.Background technology
Cerium zirconium compound oxide is in catalysis material, sensor material, electrode material, optical material, semi-conducting material, fuel
The fields such as battery, structural material, high-strength ceramic and material of cooling are with a wide range of applications.But with regard to cerium zirconium compound oxide
Large-scale application from the point of view of, catalytic field, the especially application in catalytic cleaning of car tail gas field are also concentrated mainly at present
Show day and project.Meanwhile, cerium zirconium compound oxide except the three-effect catalysis agent key coating material administered as motor-vehicle tail-gas it
Outward, RE treatment steel is at aspects such as resource abundance, cost, preparation technology and performances, all with stronger advantage.It is dilute at present
Native catalyst field of energy environment be mainly used in purifying vehicle exhaust, industrial waste gas and human settlement purification, catalysis burning and
Several aspects such as fuel cell.Especially in terms of industrial waste gas, human settlement's purification.It is latent with huge application market and development
Power.
In the three-way catalyst that motor-vehicle tail-gas are administered, it is usually added into CeO2 or the solid solution containing Ce and stores agent as oxygen
To improve the oxygen storage capacity of catalyst, so as to improve the catalytic performance of three-way catalyst.But the catalyst is in high temperature ageing
Afterwards catalytic performance declines to a great extent, this mainly decline to a great extent with the specific surface area of catalyst in high temperature it is relevant, so being changed using doping
Come to improve its high high-temp stability be most straightforward approach, wherein Ce-Zr-O systems show good heat stability and oxygen to property
Change reducing property, so its catalytic performance is more superior, study also extensive.
Due to adding after Zr in CeO2, the part Ce in former lattice is replaced by Zr, and the radius of Zr ions is less than Ce
The radius of ion, CeO2 face-centred cubic structures cause lattice structure to be distorted because of Lattice Contraction, generate face-centered cubic defect,
The mobility of negative oxygen ion in so as to considerably increase fluorite lattice, makes storage oxygen and the ability of release oxygen be greatly improved,
Improve catalysis activity.Simultaneously because single CeO2 experience high temperature (>Can 1023K) make sintering itself and reduce catalysis and make
With, the use not being suitable under hot conditionss, and the high temperature that the incorporation of Zr with stable cubic fluorite structure, can improve catalyst is steady
Qualitative, the anti-caking power for making catalyst is improved.So Ce-Zr-O systems just have the advantage that as storage oxygen catalysis material:Ce-
Zr-O systems storage oxygen occurs at low temperatures, the CO in vehicle exhaust so can be made to be completely converted into CO2 at low temperature, this
Sample just improves the air-fuel ratio characteristic of catalyst, promotes dispersion of the noble metal in catalyst surface, so as to improve the heat of carrier
Stability and promotion steam conversion reaction, may finally improve the reactivity of three-way catalyst.
The third element portions is introduced in Ce-Zr-O systems and replaces Ce ions, can further deepen the journey of lattice defect
Degree, so as to improve its catalysis storage oxygen effect.It is wherein again in the majority with rare earth doped element, mainly there are La, Y, Tb, Gd and Pr etc. [8],
These ions are introduced in Ce-Zr-O lattices can form multivariate solid solution, because the ion doping of different scale causes Ce-Zr-O brilliant
There is different degrees of distortion in lattice, this will cause Oxygenous activity to strengthen, so as to significantly improve the oxidation of Ce-Zr-O systems
Reducing property.And the non-rare earth that adulterates can also bring the effect above, what such as Mn, Cu, Ba element can also be different degrees of makes
Ce-Zr-O system distortions of lattice, while they are easily formed lattice surface defect, so as to improve the absorbability to oxygen.Extremely
The present introduces the third element formation ternary solid solution in Ce-Zr-O systems and further improves oxygen storage capacity and high high-temp stability
One of study hotspot is become.
ZL200510115874.2 discloses a kind of solid solution composition of cerium zirconium compound oxide with high specific surface and its preparation
Method.The invention adds surfactant or amine salt or inorganic ammonium salt or ethanol by being added in the suspension being settled out, and
High temperature crystallization, product Jing washing with alcohol, high-temperature roasting after crystallization..
CN101637721B discloses a kind of porous yttrium-cerium-zirconium solid solution and preparation method thereof.The invention is by adding protection
Agent, norium saline solution and active polystyrene microsphere emulsion, room temperature precipitation, 80-100 DEG C of ageing, collection precipitate,
Washing, dry, roasting obtain target product.
CN100496745C discloses a kind of wire or rod-like polycrystal Ce0.6Zr0.3Y0.1O2 solid solution preparations. and should
Patent is used as surfactant by adding cetyl trimethylammonium bromide, and by hydrothermal treatment consists presoma is obtained, and calcination obtains mesh
Mark product.
The patent of invention and U.S. patents number of United States Patent (USP) US5,747,401 is the patent of invention of US5,723,101
Disclose and mixed sediment obtained using altogether hydrothermal decomposition method or coprecipitation, then washed with alkyl oxide solution or
Dipping, obtains solid solution and has high-ratio surface, uniform particle distribution and high oxygen storage power.Cerium solution used (can be by electricity for tetravalence
Solution oxidation, cerous nitrate ammonia or dissolving carbonate add hydrogen peroxide to obtain), Ce4+ concentration be more than 85%, 900 DEG C, 6 hours specific surfaces:
51.7m2/g。
The patent of invention of United States Patent (USP) US6,133,194 disclose one kind prepare cerium oxide, Zirconium oxide, cerium zirconium be combined
Oxide or cerium zirconium sosoloid, with fine granularity distribution, high-ratio surface, high the performance of oxygen is stored.The performance is to prepare
Add what additive was realized in journey.In intermediate processing embodiment, additive is added in cerium zirconium feed liquid or in ammonia precipitation process agent, multiple
900 DEG C of compound Jing, 6 hours aging rear specific surfaces are 35m2/g.
The patent of invention of Chinese patent CN1470455A discloses composite cerium-zirconium-barium oxides and preparation method thereof, its feature
Be with cerous nitrate, zirconium nitrate, barium nitrate as raw material, by metal saline solution add polyethylene glycol polymer coating material,
It is obtained using n-butyl alcohol azeotropic distillation.Gained complex is in nanoscale, good dispersion.But as a upper patent, cost is too
Cross, be not suitable for large-scale production.
The patent of invention of Chinese patent CN1565722A discloses co-precipitation preparation cerium zirconium under cationic surfactant and consolidates
The method of solution, be characterized in introducing cationic surfactant (such as cetyl trimethylammonium bromide), Jing oil baths it is long when
Between ageing, last Organic substance (such as acetone) embathe, dry, calcining.Gained sample roasting at 950 DEG C, specific surface is 58m2/g.
The patent of invention of Chinese patent CN101607195A discloses a kind of simple coprecipitation method and prepares nanoscale cerium zirconium
Solid solution, the lanthanum cerium zirconium for being obtained (30%CeO2-60%ZrO2-10%La2O3, weight ratio) sample roasting 8 at 1100 DEG C
Hour, specific surface is 21m2/g.
At present in terms of the research of Ce-Zr based composite oxide, being primarily directed to cerium zirconium carries out further study on the modification,
Discussion of selection and mechanism of modification including modifying element etc..What is carried throughout is the structural characterization with regard to its synthetic method, and
Composition, between structure and OSC, heat stability relation research.
But the use of Ce-Zr based composite oxide catalysis material, in addition to using as coating material, needs according to not
Same application mode carries out using the adjustment of technique, especially net in industrial waste gas and human settlement such as in field of energy environment
The occupation mode for considering cerium zirconium compound oxide is needed in the fields such as change, petrochemical industry, such as whether need specific shape,
The aspect such as crushing resistance or wear resistence is appeared in the newspapers announcement.
The content of the invention
It is an object of the invention to provide a kind of Ce-Zr based composite oxide catalysis material and preparation method thereof, existing to overcome
There is the deficiency of technology.
Described Ce-Zr based composite oxide catalysis material, it is characterised in that it is to store up oxygen by cerium zirconium based solid solution rare earth
Material, Kaolin and aluminium oxide composition.
Preferably, the pattern of described Ce-Zr based composite oxide catalysis material is spherical;
Preferably, described Ce-Zr based composite oxide catalysis material, percentage by weight is as follows:
Cerium zirconium based solid solution rare earth oxygen storage material 50-70%
Kaolin 10-30%
Aluminium oxide 10-30%
Preferably, described cerium zirconium based solid solution rare earth oxygen storage material, percentage by weight is as follows:
Cerium oxide 30-60%;
Zirconium oxide 25-65%;
Except cerium other rare earth oxides 5-15%.
The one kind of other rare earth oxides of described except cerium in lanthana, yittrium oxide, praseodymium oxide and Dineodymium trioxide
More than;
The preparation method of described Ce-Zr based composite oxide catalysis material, comprises the steps:
(1) preparation of cerium zirconium based solid solution rare earth oxygen storage material:
The preparation of active component feed liquid A:
Cerous nitrate, the soluble nitrate of other rare earths of except cerium and zirconium nitrate are dissolved in into water, chelating agent is added, so
Post-heating obtains active component feed liquid A to 60-90 DEG C of reaction 1-2h;
Described chelating agent is a kind of in citric acid, ammonium citrate, and the addition of chelating agent is cerous nitrate, except cerium
Other rare earth soluble nitrates and zirconium nitrate gross mass 10~20%;
The preparation of cerium zirconium based solid solution rare earth oxygen storage material presoma:
With the ammonia that weight concentration is 10~25% as precipitant, in being added to 60-90 DEG C of active component feed liquid A,
It is 8-9 to pH, is incubated 2-4h, washing, dehydration obtains cerium zirconium based solid solution rare earth oxygen storage material presoma;
The surface treatment of zirconio solid solution rare earth oxygen storage material presoma:
Described cerium zirconium based solid solution rare earth oxygen storage material presoma is mixed into dispersion with surface conditioning agent;
The surface conditioning agent is described selected from the combination of one or more in lauric acid, stearic acid or alkenyl succinic anhydride
The addition of surface conditioning agent is the gross mass of cerous nitrate, other rare earth soluble nitrates of except cerium and zirconium nitrate
30-50%.
Roasting:
By surface treated cerium zirconium based solid solution rare earth oxygen storage material presoma at 550-750 DEG C roasting 4-8h,
The cerium zirconium based solid solution rare earth oxygen storage material can be obtained;
In active component feed liquid A, the percentage by weight of each nitrate is:
Cerous nitrate 20-50%
Zirconium nitrate 40-76%
Other rare earths soluble nitrate 3-12% of except cerium.
The percentage ratio sum of component is 100%;
(2) preparation of Ce-Zr based composite oxide catalysis material
By Alumina gel, Kaolin, cerium zirconium based solid solution rare earth oxygen storage material and water that alumina weight solid content is 10%
Beating, is made into slurry of the treatment solid content total amount for 30-50%, and shearing disperses 0.5-1h, ball milling 0.5-1h, then Jing spray dried
It is dry, then solidify in calcining kiln, you can prepare described Ce-Zr based composite oxide catalysis material.
Described spray drying, the shower nozzle of spray dryer is rotating disk;The condition of spray drying be in-furnace temperature 500~
550 DEG C, 250~260 DEG C of outlet temperature, 4~6MPa of pressure.
Described solidification, it is characterised in that condition of cure is 550-650 DEG C of 3-4h.
The Ce-Zr based composite oxide catalysis material of the present invention, compared with prior art, with specific surface area is big, high temperature resists
Aging ability it is good and store oxygen ability it is high the features such as, while with mechanical strengths such as good crushing resistance, wear resistences, it is adaptable to work
The exhaust-gas treatments such as industry waste gas, human settlement's purification and petrochemical industry.
Description of the drawings
Fig. 1 is the XRD schematic diagrams that embodiments of the invention 1 prepare cerium zirconium based solid solution rare earth oxygen storage material.
Fig. 2 is the SEM schematic diagrams that embodiments of the invention 1 prepare Ce-Zr based composite oxide catalysis material.
Fig. 3 is the SEM schematic diagrams that the comparative example 1 of the present invention prepares Ce-Zr based composite oxide catalysis material.
Specific embodiment
Embodiment 1
480g cerous nitrates, 400g zirconium nitrates, 60g Lanthanum (III) nitrates, 60g Yttrium trinitrates are dissolved in 19000g deionized waters, are added
200g citric acids, are heated to 90 DEG C of insulation 2h, obtain active component feed liquid A;By 25% industrial ammonia and pure water with mass ratio 1:2
Mixing, obtain precipitant, by precipitant be slowly added to 90 DEG C of active component feed liquids A to pH value be 9, be incubated 2h, washing, dehydration,
Obtain cerium zirconium based solid solution rare earth oxygen storage material presoma;By the cerium zirconium based solid solution rare earth oxygen storage material presoma after dehydration with
500g lauric acids mix, and shearing dispersion, roasting 4h at 750 DEG C obtains 310g cerium zirconium based solid solution rare earth oxygen storage materials.The cerium zirconium base
Solid solution rare earth oxygen storage material is consisted of:Cerium oxide 60%, zirconium oxide 50%, lanthana 6.5%, yittrium oxide 6.5%.Cerium zirconium
The specific surface of based solid solution rare earth oxygen storage material is 100.55m2·g-1, cerium zirconium based solid solution rare earth oxygen storage material is taken in 1000 DEG C
Specific surface is 55.32m after roasting 4h2·g-1, specific surface is 35.32m after 1050 DEG C of roasting 12h2·g-1。
70g cerium zirconium based solid solution rare earth oxygen storage materials, 20g Kaolin, aluminum that 100g aluminium oxide solid contents are 10% is molten
Glue, the beating of 143g pure water, are made into the slurry that solid content total amount is 30%, and shearing disperses 0.5h, ball milling 0.5h, then Jing stoves interior temperature
500 DEG C of degree, 250 DEG C of outlet temperature, the spraying machine with rotating disk shower nozzle of pressure 4MPa is spray-dried, then in 550 DEG C of roastings
Solidify 3h in kiln, Ce-Zr based composite oxide catalysis material is obtained.
Embodiment 2
200g cerous nitrates, 770g zirconium nitrates, 30g Lanthanum (III) nitrates are dissolved in 19000g deionized waters, add 100g ammonium citrates,
60 DEG C of insulation 1h are heated to, active component feed liquid A is obtained;By 10% industrial ammonia and pure water with mass ratio 1:2 mixing, must precipitate
Agent, by precipitant be slowly added to 60 DEG C of active component feed liquids A to pH value be 8, be incubated 4h, washing, dehydration, obtain cerium zirconium base solid solution
Body rare earth oxygen storage material presoma;Cerium zirconium based solid solution rare earth oxygen storage material presoma after dehydration is mixed with 300g lauric acids
Close, shearing dispersion, roasting 8h at 550 DEG C obtains 242g cerium zirconium based solid solution rare earth oxygen storage materials.The cerium zirconium based solid solution rare earth storage
Oxygen material is consisted of:Cerium oxide 30%, zirconium oxide 60%, lanthana 5%.The ratio table of cerium zirconium based solid solution rare earth oxygen storage material
Face is 120.18m2·g-1, it is 55.86m to take cerium zirconium based solid solution rare earth oxygen storage material specific surface after 1000 DEG C of roasting 4h2·g-1, specific surface is 37.38m after 1050 DEG C of roasting 12h2·g-1。
50g cerium zirconium based solid solution rare earth oxygen storage materials, 30g Kaolin, aluminum that 200g aluminium oxide solid contents are 10% is molten
Glue, the beating of 53g pure water, are made into the slurry that solid content total amount is 30%, and shearing disperses 1h, ball milling 1h, then Jing in-furnace temperatures 550
DEG C, 260 DEG C of outlet temperature, the spraying machine with rotating disk shower nozzle of pressure 6MPa is spray-dried, then solid in 650 DEG C of calcining kilns
Change 6h, Ce-Zr based composite oxide catalysis material is obtained.
Embodiment 3
200g cerous nitrates, 700g zirconium nitrates, 50g Lanthanum (III) nitrates, 50g Yttrium trinitrates are dissolved in 19000g deionized waters, are added
300g citric acids, are heated to 80 DEG C of insulation 3h, obtain active component feed liquid A;By 15% industrial ammonia and pure water with mass ratio 1:2
Mixing, obtains precipitant, by precipitant be slowly added to 80 DEG C of active component feed liquids A to pH value is 8.5, be incubated 3h, it is washing, de-
Water, obtains cerium zirconium based solid solution rare earth oxygen storage material presoma;By the cerium zirconium based solid solution rare earth oxygen storage material presoma after dehydration
Mix with 400g lauric acids, shearing dispersion, roasting 4h at 700 DEG C obtains 254 cerium zirconium based solid solution rare earth oxygen storage materials.The cerium zirconium
Based solid solution rare earth oxygen storage material is consisted of:Cerium oxide 30%, zirconium oxide 55%, lanthana 7.5%, yittrium oxide 7.5%.Cerium
The specific surface of zirconio solid solution rare earth oxygen storage material is 100.02m2·g-1, cerium zirconium based solid solution rare earth oxygen storage material is taken in 1000
Specific surface is 51.28m after DEG C roasting 4h2·g-1, specific surface is 33.12m after 1050 DEG C of roasting 12h2·g-1。
60g cerium zirconium based solid solution rare earth oxygen storage materials, 30g Kaolin, aluminum that 100g aluminium oxide solid contents are 10% is molten
Glue, the beating of 10g pure water, are made into the slurry that solid content total amount is 50%, and shearing disperses 1h, ball milling 1h, then Jing in-furnace temperatures 550
DEG C, 260 DEG C of outlet temperature, the spraying machine with rotating disk shower nozzle of pressure 5MPa is spray-dried, then solid in 600 DEG C of calcining kilns
Change 3.5h, Ce-Zr based composite oxide catalysis material is obtained.
Embodiment 4
480g cerous nitrates, 400g zirconium nitrates, 60g praseodymium nitrates, 60g neodymium nitrates are dissolved in 19000g deionized waters, are added
200g citric acids, are heated to 90 DEG C of insulation 2h, obtain active component feed liquid A;By 20% industrial ammonia and pure water with mass ratio 1:2
Mixing, obtain precipitant, by precipitant be slowly added to 90 DEG C of active component feed liquids A to pH value be 9, be incubated 2h, washing, dehydration,
Obtain cerium zirconium based solid solution rare earth oxygen storage material presoma;By the cerium zirconium based solid solution rare earth oxygen storage material presoma after dehydration with
500g lauric acids mix, and shearing dispersion, roasting 4h at 750 DEG C obtains 310g cerium zirconium based solid solution rare earth oxygen storage materials.The cerium zirconium base
Solid solution rare earth oxygen storage material is consisted of:Cerium oxide 60%, zirconium oxide 50%, praseodymium oxide 6.5%, Dineodymium trioxide 6.5%.Cerium zirconium
The specific surface of based solid solution rare earth oxygen storage material is 109.55m2·g-1, cerium zirconium based solid solution rare earth oxygen storage material is taken in 1000 DEG C
Specific surface is 59.32m after roasting 4h2·g-1, specific surface is 38.32m after 1050 DEG C of roasting 12h2·g-1。
70g cerium zirconium based solid solution rare earth oxygen storage materials, 20g Kaolin, aluminum that 100g aluminium oxide solid contents are 10% is molten
Glue, the beating of 143g pure water, are made into the slurry that solid content total amount is 30%, and shearing disperses 0.5h, ball milling 0.5h, then Jing stoves interior temperature
500 DEG C of degree, 250 DEG C of outlet temperature, the spraying machine with rotating disk shower nozzle of pressure 4MPa is spray-dried, then in 550 DEG C of roastings
Solidify 3h in kiln, Ce-Zr based composite oxide catalysis material is obtained.
Comparative example 1
480g cerous nitrates, 400g zirconium nitrates, 60g Lanthanum (III) nitrates, 60g Yttrium trinitrates are dissolved in 19000g deionized waters, are added
200g citric acids, are heated to 90 DEG C of insulation 2h, obtain active component feed liquid A;By 25% industrial ammonia and pure water with mass ratio 1:2
Mixing, obtain precipitant, by precipitant be slowly added to 90 DEG C of active component feed liquids A to pH value be 9, be incubated 2h, washing, dehydration,
Obtain cerium zirconium based solid solution rare earth oxygen storage material presoma;By the cerium zirconium based solid solution rare earth oxygen storage material presoma after dehydration with
500g lauric acids mix, and shearing dispersion, roasting 4h at 750 DEG C obtains 310g cerium zirconium based solid solution rare earth oxygen storage materials.The cerium zirconium base
Solid solution rare earth oxygen storage material is consisted of:Cerium oxide 60%, zirconium oxide 50%, lanthana 6.5%, yittrium oxide 6.5%.Cerium zirconium
The specific surface of based solid solution rare earth oxygen storage material is 100.55m2·g-1, cerium zirconium based solid solution rare earth oxygen storage material is taken in 1000 DEG C
Specific surface is 55.32m after roasting 4h2·g-1, specific surface is 35.32m after 1050 DEG C of roasting 12h2·g-1。
70g cerium zirconium based solid solution rare earth oxygen storage materials, 20g Kaolin, aluminum that 100g aluminium oxide solid contents are 10% is molten
Glue, the beating of 143g pure water, are made into the slurry that solid content total amount is 30%, and shearing disperses 0.5h, ball milling 0.5h, then Jing stoves interior temperature
500 DEG C of degree, 350 DEG C of outlet temperature, the spraying machine with rotating disk shower nozzle of pressure 4MPa is spray-dried, then in 550 DEG C of roastings
Solidify 3h in kiln, Ce-Zr based composite oxide catalysis material is obtained.
The ultimate principle and principal character and advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel it should be appreciated that the present invention is not restricted to the described embodiments, the simply explanation described in above-described embodiment and description this
The principle of invention, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, these changes
Change and improvement both fallen within scope of the claimed invention, the claimed scope of the invention by appending claims and its
Equivalent thereof.
Claims (3)
1. Ce-Zr based composite oxide catalysis material, it is characterised in that pattern is spherical, and percentage by weight is as follows:
Cerium zirconium based solid solution rare earth oxygen storage material 50-70%
Kaolin 10-30%
Aluminium oxide 10-30%
Described cerium zirconium based solid solution rare earth oxygen storage material, the percentage by weight of each component is as follows:
Cerium oxide 30-60%;
Zirconium oxide 25-65%;
Except cerium other rare earth oxides 5-15%
Other rare earth oxides of except cerium are selected from one or more of lanthana, yittrium oxide, praseodymium oxide and Dineodymium trioxide;
Preparation method, comprises the steps:
(1) preparation of cerium zirconium based solid solution rare earth oxygen storage material:
1. the preparation of active component feed liquid A:
Cerous nitrate, the soluble nitrate of other rare earths of except cerium and zirconium nitrate are dissolved in into water, chelating agent, Ran Houjia is added
Heat obtains active component feed liquid A to 60-90 DEG C of reaction 1-2h;
Described chelating agent is a kind of in citric acid, the ammonium citrate, the addition of chelating agent be cerous nitrate, except cerium its
The 10~20% of the gross mass of his rare earth soluble nitrate and zirconium nitrate;
2. the preparation of cerium zirconium based solid solution rare earth oxygen storage material presoma:
With the ammonia that weight concentration is 10~25% as precipitant, in being added to 60-90 DEG C of active component feed liquid A, to pH
For 8-9,2-4h is incubated, washing, dehydration obtain cerium zirconium based solid solution rare earth oxygen storage material presoma;
3. the surface treatment of zirconio solid solution rare earth oxygen storage material presoma:
Described cerium zirconium based solid solution rare earth oxygen storage material presoma is mixed into dispersion with surface conditioning agent;
The surface conditioning agent is selected from the combination of one or more in lauric acid, stearic acid or alkenyl succinic anhydride, the surface
The addition of inorganic agent is cerous nitrate, the 30- of the gross mass of other rare earth soluble nitrates and zirconium nitrate of except cerium
50%;
4. roasting:
By surface treated cerium zirconium based solid solution rare earth oxygen storage material presoma at 550-750 DEG C roasting 4-8h, you can
Obtain the cerium zirconium based solid solution rare earth oxygen storage material;
In active component feed liquid A, the percentage by weight of each nitrate is:
Cerous nitrate 20-50%
Zirconium nitrate 40-76%
Other rare earths soluble nitrate 3-12% of except cerium
The percentage ratio sum of component is 100%;
(2) preparation of Ce-Zr based composite oxide catalysis material
By Alumina gel, Kaolin, cerium zirconium based solid solution rare earth oxygen storage material and water beating that alumina weight solid content is 10%,
The slurry that weight solid content total amount is 30-50% is made into, shearing dispersion 0.5-1h, ball milling 0.5-1h are then spray-dried, so
Solidify in calcining kiln afterwards, you can prepare described Ce-Zr based composite oxide catalysis material.
2. Ce-Zr based composite oxide catalysis material according to claim 1, it is characterised in that described spray drying,
The shower nozzle of spray dryer is rotating disk;The condition of spray drying be 500~550 DEG C of in-furnace temperature, 250~260 DEG C of outlet temperature,
4~6MPa of pressure.
3. Ce-Zr based composite oxide catalysis material according to claim 1, it is characterised in that in step (2), solidified bars
Part is 550-650 DEG C of 3-4h.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410634981.5A CN104437458B (en) | 2014-11-12 | 2014-11-12 | Cerium-zirconium-based composite oxide catalytic material and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410634981.5A CN104437458B (en) | 2014-11-12 | 2014-11-12 | Cerium-zirconium-based composite oxide catalytic material and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104437458A CN104437458A (en) | 2015-03-25 |
CN104437458B true CN104437458B (en) | 2017-05-17 |
Family
ID=52884667
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410634981.5A Active CN104437458B (en) | 2014-11-12 | 2014-11-12 | Cerium-zirconium-based composite oxide catalytic material and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104437458B (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105080530A (en) * | 2015-05-26 | 2015-11-25 | 华东理工大学 | Preparation method for cerium-zirconium composite oxide with high performance |
CN108408757B (en) * | 2018-03-15 | 2020-06-23 | 益阳鸿源稀土有限责任公司 | Preparation method of high-purity superfine scandium oxide powder |
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 |
CN114177902B (en) * | 2021-12-14 | 2023-09-15 | 西华师范大学 | Cerium-zirconium solid solution with micron-sized macropores and preparation method and application thereof |
CN117586755B (en) * | 2024-01-19 | 2024-04-09 | 镧明材料技术(上海)有限公司 | Refrigerating material and preparation method and application thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103084161A (en) * | 2011-11-04 | 2013-05-08 | 上海华明高纳稀土新材料有限公司 | Ce-Zr-Al-based composite oxide rare earth oxygen-storage material and preparation method thereof |
CN103127925A (en) * | 2011-11-23 | 2013-06-05 | 上海华明高纳稀土新材料有限公司 | Cerium-zirconium-based solid solution rare earth oxygen-storage material and preparation method thereof |
-
2014
- 2014-11-12 CN CN201410634981.5A patent/CN104437458B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103084161A (en) * | 2011-11-04 | 2013-05-08 | 上海华明高纳稀土新材料有限公司 | Ce-Zr-Al-based composite oxide rare earth oxygen-storage material and preparation method thereof |
CN103127925A (en) * | 2011-11-23 | 2013-06-05 | 上海华明高纳稀土新材料有限公司 | Cerium-zirconium-based solid solution rare earth oxygen-storage material and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN104437458A (en) | 2015-03-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104437458B (en) | Cerium-zirconium-based composite oxide catalytic material and preparation method thereof | |
JP5063252B2 (en) | Porous zirconia-based powder and method for producing the same | |
EP1894620B1 (en) | Porous zirconia powder and production method of same | |
EP1803686B1 (en) | Cerium-zirconium mixed oxide and method for manufacturing the same | |
CN100584762C (en) | Zirconium and yttrium oxide-based composition, method for preparing same and use thereof in a catalyst system | |
CN102580719B (en) | Nanometer ceria-zirconium solid solution and preparation method thereof | |
JP3341973B2 (en) | Oxide solid solution particles and method for producing the same | |
JP5564109B2 (en) | Composition comprising cerium oxide and zirconium oxide with specific porosity, its preparation method and its use in catalysis | |
CN103191712A (en) | Cerium oxide and zirconium oxide based composite rare earth oxide with favorable ageing resistance and high reduction activity and preparation method of cerium oxide and zirconium oxide based composite rare earth oxide | |
KR20130000419A (en) | Composition containing oxides of zirconium, cerium and at least one other rare earth and having a specific porosity, method for preparing same and use thereof in catalysis | |
CN109529801A (en) | Controllable double hole channel cerium zirconium compound oxide and its preparation method and application | |
KR20140033116A (en) | Ceria zirconia alumina composition with enhanced thermal stability | |
CN106824163B (en) | Composite oxides and preparation method thereof | |
CN101827651A (en) | Rare earth alumina particulate manufacturing method and application | |
CN103191711A (en) | Cerium oxide-zirconium oxide based composite rare-earth oxide with high specific surface area and high oxygen storage capacity and preparation method thereof | |
CN103084161A (en) | Ce-Zr-Al-based composite oxide rare earth oxygen-storage material and preparation method thereof | |
CN104528799B (en) | A kind of preparation method of magnesio rare earth hexa-aluminate superfine powder | |
CN106732521B (en) | Preparation method of high-performance cerium-zirconium solid solution material | |
CN102531015A (en) | Method for preparing porous aluminum oxide superfine powder | |
CN106946282A (en) | A kind of preparation method of porous cerium-based composite oxides | |
CN103263911B (en) | Preparation method of denitration catalyst with nanoscale ordered honeycomb structure | |
EP2781487B1 (en) | Composite oxide | |
CN101074490B (en) | Method for producing spherical, tie-shaped and octahedral polycrystalline Ce0.6Zr0.3Y0.1O2 particles of um sizes | |
CN101269832A (en) | Process for producing nano-cerium dioxide with high-specific surface area and high hole capacity | |
CN108187665A (en) | Denitrating catalyst and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |