CN110026176A - A kind of cerium zirconium compound oxide, preparation method and application - Google Patents
A kind of cerium zirconium compound oxide, preparation method and application Download PDFInfo
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Abstract
This application discloses a kind of cerium zirconium compound oxides and preparation method thereof, belong to adsorption catalyst field.The preparation method of the cerium zirconium compound oxide includes the following steps: 1) mixing: raw material is made to the first mixed object of the strong acid aqueous solution of the metal including at least cerium ion and zirconium ion；2) the first hydro-thermal reaction: alkaline precipitating agent is added into first mixed object, the acid-mixed object that pH value is 1-6 is made, the acid-mixed object is subjected to the first hydro-thermal reaction, precursor solution is made；3) the second hydro-thermal reaction: alkaline precipitating agent is added into precursor solution, pH value is made is that 8-11 alkali mixes object, will carry out filtering, washing and calcining after the second hydro-thermal reaction, obtains the cerium zirconium compound oxide.The anti-aging property of cerium zirconium compound oxide made from this method is good, particle diameter distribution is uniform, oxygen storage capacity is high low with reduction temperature.
Description
Technical field
This application involves a kind of cerium zirconium compound oxides and preparation method thereof, belong to adsorption catalyst field.
Background technique
Cerium zirconium compound oxide is mainly used in the tail gas catalyzed field of moving source, plays the work of catalyst carrier and auxiliary agent
With, since working environment reaches as high as 1000 DEG C, cerium zirconium compound oxide need to have excellent anti-aging property to protect
The utilization efficiency of noble metal is demonstrate,proved, the higher catalytic activity of catalyst is maintained.
Anti-aging property under cerium zirconium compound oxide hot conditions, i.e., compound ratio still with higher after high temperature ageing
Surface area, Kong Rong and suitable cellular structure.The physical and chemical indexes of cerium zirconium compound oxide specifically include that specific surface area, Kong Rong
With aperture etc.；Functional attributes mainly include oxygen storage capacity and reduction temperature；Mainly include using index pollutant catalytic conversion,
Minimum initiation temperature and service life etc..Key core index is anti-aging property, oxygen storage capacity and the reduction temperature of material, three
In item key core index, anti-aging property is particularly important.What is played a major role in three-element catalytic is noble metal, is accounted for entire
70% or more of catalysis system cost.Noble-metal-supported amount is in 2-3% or so, but its utilization rate only has 2% or so, therefore, cerium
Zirconium mixed oxide is as carrier, and lower specific surface loss late can guarantee expensive under good anti-aging property and hot conditions
The utilization efficiency of metal, to extend the service life of catalyst.
Summary of the invention
In order to solve the above technical problems, this application provides a kind of cerium zirconium compound oxides and its preparation method and application.
Anti-aging property under the hot conditions of cerium zirconium compound oxide made from the preparation method is good, particle diameter distribution uniformly, oxygen storage capacity
It is high low with reduction temperature.
The preparation method of the cerium zirconium compound oxide, which is characterized in that it includes the following steps:
1) raw material mixing: is made to the first mixed object of the strong acid aqueous solution of the metal including at least cerium ion and zirconium ion；
2) the first hydro-thermal reaction: alkaline precipitating agent is added into first mixed object, the acid-mixed object that pH value is 1-6 is made, by the acid
Mixed object carries out the first hydro-thermal reaction, and precursor solution is made；
3) the second hydro-thermal reaction: alkaline precipitating agent is added into precursor solution, pH value is made is that 8-11 alkali mixes object, will be into
Filtering, washing and calcining after the second hydro-thermal reaction of row obtain the cerium zirconium compound oxide.
Optionally, the raw material further includes Zn, Ga, Ag, Mo, Cu, Fe, Ni, V, In, Nb, Co, Cr, Mn, La, Pr, Nd, Y
Or at least one of other rare earth elements.Preferably, the raw material further includes at least one of La, Pr and Y element.It is more excellent
Selection of land, the raw material are cerium salt, zirconates and at least one of selected from lanthanum salt, praseodymium salt and yttrium salt.Further, the cerium salt is
Ammonium ceric nitrate, the zirconates are zirconium nitrate or aluminium zirconium oxide, and the praseodymium salt is praseodymium nitrate, and the lanthanum salt is lanthanum nitrate, the yttrium
Salt is yttrium nitrate.
In a preferred embodiment, cerium zirconium compound oxide further includes the oxidation of other rare earth elements except cerium
Object, it is preferable that one of lanthana, yttrium oxide, praseodymium oxide are any several.Cerium oxide, zirconium oxide, lanthana, praseodymium oxide and
Yttrium oxide can be respectively with CeO2、ZrO2、La2O3、Pr6O11And Y2O3Form provide.
Further, the cerium zirconium compound oxide includes the CeO that weight ratio is 30-50:40-60:3-7:3-72、ZrO2、
La2O3And Pr6O11.Preferably, the weight composition of the cerium zirconium compound oxide includes 40%CeO2, 50%ZrO2, 5%La2O3、
5%Pr6O11。
Further, the cerium zirconium compound oxide includes the CeO that weight ratio is 10-30:50-70:1-5:7.5-172、
ZrO2、La2O3And Y2O3.Preferably, the weight composition of the cerium zirconium compound oxide includes 24%CeO2, 60%ZrO2, 3.5%
La2O3And 12.5%Y2O3。
Optionally, the pH value of the acid-mixed object is 1.5-2.5.Preferably, the pH value of the acid-mixed object is 1.5-2.
Optionally, the temperature of first hydro-thermal reaction is 110-300 DEG C, and the time is at least 8h.Preferably, described second
The temperature of hydro-thermal reaction is the time 8-30h at 130 DEG C -250 DEG C.
Optionally, the temperature of second hydro-thermal reaction is 110-300 DEG C, and the time is at least 6h.Preferably, described second
The temperature of hydro-thermal reaction is the time 6-20h at 130 DEG C -240 DEG C.
Optionally, the calcining in the step 3) includes: and is warming up to 200-350 DEG C with the rate of 10-70 DEG C/h to keep extremely
Few 2h, is warming up to 500-1000 DEG C of heat preservation at least 2h with the rate of 50-150 DEG C/h.
Preferably, the calcining in the step 3) includes: to be warming up to 250-300 DEG C of holding 3- with the rate of 20-60 DEG C/h
7h is warming up to 700-950 DEG C of heat preservation 3-8h with the rate of 70-120 DEG C/h.
It is highly preferred that the calcining in the step 3) includes: to be warming up to 280 DEG C of holding 3h with the rate of 35 DEG C/h, with 90
DEG C/rate of h is warming up to 950 DEG C of heat preservation 6h.The calcination condition can both guarantee the uniform volatilization of organic matter, prevent duct because having
The volatilization of machine object is too fast to be caused to collapse, and the crystal grain of cerium zirconium compound oxide can be controlled within limits, is reduced simultaneously
The defect on solid solution pellet surface prevents solid solution undue agglomeration in calcination process, specific surface is caused to decline.The table of solid solution
Planar defect position is the major surfactant position of carrier, and Adsorption is more, and carrier surfactant is higher, easier to be agglomerated into
Bulky grain；Meanwhile solid solution pellet is smaller, interfacial energy is higher, the easier reunion of particle.The calcination condition of the application
Not only the granular size of solid solution can be controlled within the scope of certain, but also the more complete of grain growth can be made, thus
Its surface-active is reduced, its undue agglomeration in subsequent ageing process is inhibited, to promote its anti-aging property.
Optionally, the air mass flow of the calcining in the step 3) is 5-30L/min/kg oxide, and the gas is selected from
Air or non-active gas.Preferably, the air mass flow of the calcining in the step 3) is 10-20L/min/kg oxide.It is excellent
Selection of land, the gas are non-active gas, and the non-active gas is selected from nitrogen or argon gas.The calcining of cerium zirconium powder prepares cerium zirconium
The dumping process of composite oxides is the process of organic matter volatilization or smoulder removal, and gas flow is excessive, waves in calcining furnace
The organic matter of hair or other solvents can be pulled away rapidly, and the organic matter in cerium zirconium compound oxide is caused to volatilize too fast and lead to hole
Road collapses.It is too fast that gas is passed through rate, not only will lead to organic matter or the volatilization of other solvents is too fast, also result in cerium zirconium powder
Organic matter and the air overheat of volatilization are burnt, and cause hot-spot inside cerium zirconium compound oxide, duct is caused to collapse.The application
Gas and flow velocity can guarantee the uniform volatilization of organic matter, while the burning of organic matter will not occur again, avoid solid solution body opening
The collapsing of road structure.
Optionally, the concentration of the oxide of the metal in the just mixed object is 20-100g/L.Preferably, the just mixed object
The concentration of the oxide of middle metal is 30-80g/L.It is highly preferred that the concentration of the oxide of metal is 40g/ in the just mixed object
L.The few surface defects of the crystal of cerium zirconium compound oxide made from the concentration of the oxide of metal in the first mixed object, and improve
Its ageing resistance has excellent anti-aging property.
Optionally, the cleaning solution in the step 3) is organic solvent.Preferably, the organic solvent is selected from ethers, alcohol
At least one of with ketone.It is highly preferred that the organic solvent is ethers.Crystallographic grain size after second hydro-thermal reaction exists
For 10nm between 15nm, grain surface activity can be high, easy to reunite.Cerium zirconium compound oxide internal gutter structure is mainly by second level
Grain is accumulated, and the filter cake moisture content that the product of hydro-thermal reaction obtains after filters pressing/filtering is high, and about 300% or so, if directly
Drying, in hydrone dispersion process, since the surface tension of water is big, easily causes crystal grain to be reunited, and duct collapses, therefore, this
Technology is needed to wash the hydrone in solid with organic solvent, be replaced.Sediment after displacement contains a large amount of organic
Therefore object accounts for about 70% of oxide mass or so, using the calcining step of the application, can preferably control the slow of organic matter
Slow removing, protects the accumulation duct of cerium zirconium compound oxide, so that calcined cerium zirconium compound oxide surface area is bigger, it is anti-ageing
It is more preferable to change performance.
Optionally, the cerium zirconium compound oxide includes the cerium oxide and zirconium oxide of 75-100wt%, the cerium oxide and
The mass ratio of zirconium oxide is 0.25-0.9:1.Preferably, the mass ratio of the cerium oxide and zirconium oxide is 0.3-0.9:1.
Preferably, the mass ratio of the cerium oxide in the cerium zirconium compound oxide and zirconium oxide is 0.3-0.8:1.Further
Ground, the mass ratio of cerium oxide and zirconium oxide in the cerium zirconium compound oxide are 0.3-0.8:1.
Optionally, the alkaline precipitating agent is selected from least one of ammonium hydroxide, sodium hydroxide, potassium hydroxide and organic amine.
Preferably, the alkaline precipitating agent is ammonium hydroxide.
According to the another aspect of the application, a kind of cerium zirconium compound oxide, the cerium zirconium compound oxide are provided
It is prepared as any above-mentioned method or, the cerium zirconium compound oxide as made from any above-mentioned method is forged through 500-1200 DEG C
At least 1h is burnt to be made.Further, the cerium zirconium compound oxide is made through 1000-1200 DEG C of calcining at least 1h.
According to further aspect of the application, provides a kind of cerium zirconium compound oxide and preparing the application in catalyst.
In the application, cerium zirconium compound oxide refers not only to the oxide of cerium zirconium, can also be the cerium for adulterating other metals
Zirconium oxide.
In the application, just the oxide of metal refers to the first oxygen for mixing all metals that object is included and being scaled metal in mixed object
The mass-volume concentration of compound.
In the application, L/min/kg oxide refers to the body for the gas that the oxide calcining of every kilogram of metal uses per minute
Product rising amount.
In preparation method in the application occur hydro-thermal hydrolysis, hydro-thermal hydrolysis acid-mixed object can for comprising cerium, zirconium,
The clarification nitrate solution of the elements such as lanthanum, yttrium or praseodymium, presoma hydrolyze principle are as follows:
M+H2O→M(OH)X+H+(1)
M(OH)X→MOy+H2O(2)
Product after the first mixed object hydro-thermal hydrolysis of the application is the mixture of oxide and hydroxide, to make the first hydro-thermal
Generation oxide as much as possible is reacted, in the case where guaranteeing the clear situation of acid-mixed object hydrating solution, as far as possible by acid-mixed object solution
PH is adjusted to higher range, which can guarantee that solution generates oxide as much as possible after a hydro-thermal.Specifically
It adjusts pH range needs to be calculated according to salting liquid concentration of metal ions and metal Ksp, the preferred embodiment of the application
PH range be 1.5-2.0.Because reaction condition limits, the ion in solution can not complete hydrolysis precipitate, a part from
Son is still in supernatant.It is 8.0- therefore, it is necessary to which the precursor solution after the first hydro-thermal reaction is adjusted to pH with ammonium hydroxide
11.0, so that the ion in precursor solution is precipitated completely, the metal to precipitate later is mainly in the form of hydroxide
In the presence of.Second hydro-thermal reaction: it is mainly that dehydration and crystal grain are perfect that the alkali after having adjusted pH, which mixes the purpose that object carries out alkaline hydro-thermal,
Process.Alkali mixes the metal mainly presence in the form of oxide and hydroxide in object after having adjusted pH, they are cross-linked with each other, and are formed
Biggish tufted micelle.By further second hydro-thermal reaction, tufted group glue can be made further to be dehydrated, reduce and reunite, together
The more oxides of Shi Shengcheng.Defective crystal grain can further grow up by this process, supply defect, reduce subsequent
The risk further reunited in calcination process.
The beneficial effect of the application includes but is not limited to:
1. the preparation method does not need the water using resistance to strong acid according to the preparation method of the cerium zirconium compound oxide of the application
Prepared by thermal reactor, reduce preparation cost, is easy industrialization.
2. according to the cerium zirconium compound oxide of the application, the anti-aging property of the cerium zirconium compound oxide is good, particle diameter distribution
Uniformly, oxygen storage capacity is high low with reduction temperature.
3. according to application of the cerium zirconium compound oxide of the application in terms of preparing catalyst, the catalyst carried noble metal
Make antiageing effect good under the high temperature conditions afterwards, so that the utilization rate of noble metal is high.
Specific embodiment
The application is described in detail below with reference to embodiment, but the application is not limited to these embodiments.
Unless otherwise instructed, the raw material in embodiments herein and solvent are bought by commercial sources.
Analysis method is as follows in embodiments herein:
Cerium zirconium compound oxide particle diameter distribution is carried out using 3000 laser particle analyzer of Mastersizer of Malvern company
Analysis.
It is multiple that cerium zirconium is carried out using the II type automatic adsorption device of Micromeritics TriStar of Micromeritics Instrument Corp. U.S.A
Close the analysis of oxide specific surface.
The analysis of cerium zirconium compound oxide oxygen storage capacity is carried out using the ChemBET-3000 instrument of Kang Ta company.
The analysis of cerium zirconium compound oxide reduction temperature is carried out using the PCA1200-TPR instrument of Bi Aode company.
And, the reality of the application is illustrated for cerium zirconium compound oxide made from praseodymium salt or yttrium salt with cerium salt, zirconates and lanthanum salt
Mode is applied, according to a kind of embodiment of the application, the preparation method of cerium zirconium compound oxide includes the following steps:
1) mixing: and, praseodymium salt or yttrium salt, which are dissolved in water respectively and stir to clarify, is made just mixed object by cerium salt, zirconates and lanthanum salt,
Just four kinds of metal oxide total concentrations in mixed object are 20-100g/L；
2) the first hydro-thermal reaction: alkaline precipitating agent is added dropwise into first mixed object, the alkaline precipitating agent is selected from ammonium hydroxide, hydroxide
At least one of sodium, potassium hydroxide and amine, the pH for adjusting just mixed object is the acid-mixed object of 1-6, and the acid-mixed object is carried out first
Precursor solution is made in hydro-thermal reaction；
3) the second hydro-thermal reaction: alkaline precipitating agent is added into precursor solution, pH value is made is that 8-11 alkali mixes object, by alkali
Mixed object, which is placed in titanium high pressure water heating kettle, carries out the second hydro-thermal reaction, filtering, with water and organic solvent washing, calcines, sieving, i.e.,
Cerium zirconium compound oxide is made；
Wherein, the temperature of the first hydro-thermal reaction is 110-300 DEG C, and the time is at least 8h；Second hydro-thermal reaction is in temperature
6h is at least reacted at 110-300 DEG C；Calcining includes: to be warming up to 200-350 DEG C of holding at least 2h with the rate of 10-70 DEG C/h, with
The rate of 50-150 DEG C/h is warming up to 500-1000 DEG C of heat preservation at least 2h, and the air mass flow of calcining is 5-30L/min/kg oxidation
Object.
The preparation of 1 cerium zirconium compound oxide 1# of embodiment
The preparation method of the cerium zirconium compound oxide of the application is illustrated by taking cerium zirconium compound oxide 1# as an example.Cerium zirconium is multiple
Close the weight composition of the oxide of oxide 1# are as follows: 24%CeO2, 60%ZrO2, 3.5%La2O3, 12.5%Y2O3。
1) ammonium ceric nitrate and nitre mixing: are added after zirconium nitrate is dissolved in deionized water mixing with the yttrium oxide for being dissolved in concentrated nitric acid
Sour lanthanum, and stir to clarify, just mixed object is made, first mixed object is put into 10L titanium reaction kettle, compactedness 64%, oxide gross mass
256g, wherein the just oxide CeO of the metal in mixed object2、ZrO2、La2O3And Y2O3Concentration be 40g/L；
2) the first hydro-thermal reaction: first mixed object is tuned into the acid-mixed object that pH is 1.5-2.0 with ammonium hydroxide, is in temperature by acid-mixed object
190 DEG C, the first hydro-thermal reaction is carried out under conditions of time 25h, and precursor solution is made；
3) the second hydro-thermal reaction: ammonium hydroxide is added into precursor solution, pH value is made is that 8-11 alkali mixes object, and alkali is mixed object and is set
In temperature it is 170 DEG C in titanium high pressure water heating kettle, carries out the second hydro-thermal reaction under conditions of time 10h, filter, gone with 50L
It ion water washing 3 times, is washed 2 times with 560g organic matter, the organic matter recycling filtered out is calcined, and it is compound to obtain cerium zirconium for sieving
Oxide 1#；
Wherein, calcining includes: to be warming up to 280 DEG C of holding 3h with the rate of 35 DEG C/h, is warming up to 950 with the rate of 90 DEG C/h
DEG C heat preservation 6h；The air mass flow of calcining is 12L/min/kg oxide.
Aging: by cerium zirconium compound oxide 1# at 1100 DEG C aging process 4h.
The preparation and characterization of embodiment 2-10 cerium zirconium compound oxide 2#-10#
According to the preparation method of cerium zirconium compound oxide 1#, change hydrothermal condition, just mixed object concentration and calcination condition respectively
It carries out preparing cerium zirconium compound oxide 2#-10#, tests its surface area, granularity, oxygen storage capacity and reduction temperature, then respectively by cerium
Zirconium mixed oxide 2#-10# aging according to the method for embodiment 1, the surface area after testing its aging respectively.Cerium-zirconium composite oxide
The preparation method difference of object 2#-10# and cerium zirconium compound oxide 1# is as shown in table 1.
Table 1
Concentration by just mixing the metal oxide of object in table 1 it can be seen from data cerium zirconium compound oxide 2#-5# increases,
Cerium zirconium compound oxide specific surface is decreased obviously after aging, excessive concentration, and solution supersaturation is serious, can moment analysis in a short time
A large amount of nucleus out, leads to that the crystal grain finally obtained is more but size of microcrystal is smaller, has high surface-active, easily occurs
Reunite.When preparing alkali and mixing object, be added after ammonium hydroxide adjusted pH, minimum crystal grain can moment reunion, or even in higher concentrations can
Reunion glomeration causes the second final hydro-thermal reaction product cerium zirconium powder specific surface sharply to decline.By cerium zirconium compound oxide
6#-8# can be seen that in the presence of preferably hydrothermal reaction condition, and the cerium zirconium compound oxide synthesized with this condition has completeer
Whole crystal structure, plane of crystal defect is few, and calcining is not easy to reunite, and anti-aging property is excellent.
The application cerium zirconium compound oxide 9#-10# heating rate is different, it can be seen that slow heating rate can protect
The uniform volatilization of organic matter is demonstrate,proved, the cerium zirconium compound oxide calcined out has better anti-aging property.
By the test result of the granularity of cerium zirconium compound oxide 1#-10#, oxygen storage capacity and reduction temperature it is found that the application
The granularity of cerium zirconium compound oxide made from preparation method is small, and oxygen storage capacity is big and reduction temperature is low.
The preparation and characterization of 11 cerium zirconium compound oxide 11# of embodiment
Cerium zirconium compound oxide 11# is prepared according to the method for embodiment 1, the difference is that: the first hydro-thermal reaction: use ammonia
First mixed object is tuned into the acid-mixed object that pH is 3.0-4.0 by water, and acid-mixed object is carried out the first hydro-thermal reaction, precursor solution is made.System
The surface area of the cerium zirconium compound oxide 11# obtained is 87.6g/cm2, the surface area after aging is 29.8g/cm2。
The preparation and characterization of 12 cerium zirconium compound oxide 12# of embodiment
It is prepared according to the method for embodiment 1 to zirconium solid solution 12#, the difference is that: the group of cerium zirconium compound oxide 12#
Dividing includes 40%CeO2, 50%ZrO2, 5%La2O3, 5%Pr6O11.The surface area of cerium zirconium compound oxide 12# obtained is
82.17g/cm2, the surface area after aging is 36.41g/cm2, anti-aging property height.
The preparation and characterization of the comparison of comparative example 1 cerium zirconium compound oxide D1#
Comparison cerium zirconium compound oxide D1# is prepared according to the method for embodiment 1, the difference is that without the first hydro-thermal
Reaction, directly the second hydro-thermal reaction of progress, i.e., after the pH value of first mixed object being directly adjusted to 8-11, according to the method for embodiment 1
Carry out the second hydro-thermal reaction.The surface area of comparison cerium zirconium compound oxide D1# obtained is 85g/cm2, surface area after aging
For 24.3g/cm2, anti-aging property is poor.
The preparation and characterization of the comparison of comparative example 2 cerium zirconium compound oxide D2#
Comparison cerium zirconium compound oxide D2# is prepared according to the method for embodiment 1, the difference is that the air mass flow of calcining
For 35L/min/kg oxide.There is hardened phenomenon in comparison cerium zirconium compound oxide D2#.
The preparation and characterization of the comparison of comparative example 3 cerium zirconium compound oxide D3#
Comparison cerium zirconium compound oxide D3# is prepared according to the method for embodiment 1, the difference is that the washing in step 3)
Liquid is water.The surface area of comparison cerium zirconium compound oxide D3# obtained is 77.5g/cm2, the surface area after aging is 19.8g/
cm2.Compared with organic matter, the surface tension of water is larger, and collapsing for cerium zirconium compound oxide duct is easily caused in volatilization process
It collapses, so as to cause the sharply decline of cerium zirconium compound oxide ageing properties.
The above, only embodiments herein, the protection scope of the application is not by these specific embodiments
Limitation, but determined by following claims.To those skilled in the art, the application can have various
Change and variation.All any modification, equivalent replacement, improvement and so within the technical idea and principle of the application, should all
Comprising within the scope of protection of this application.
Claims (13)
1. a kind of preparation method of cerium zirconium compound oxide, which is characterized in that it includes the following steps:
1) raw material mixing: is made to the first mixed object of the strong acid aqueous solution of the metal including at least cerium ion and zirconium ion；
2) the first hydro-thermal reaction: alkaline precipitating agent is added into first mixed object, the acid-mixed object that pH value is 1-6 is made, by the acid-mixed object
The first hydro-thermal reaction is carried out, precursor solution is made；
3) the second hydro-thermal reaction: alkaline precipitating agent is added into precursor solution, pH value is made is that 8-11 alkali mixes object, will carry out the
Filtering, washing and calcining after two hydro-thermal reactions obtain the cerium zirconium compound oxide.
2. preparation method according to claim 1, which is characterized in that the pH value of the acid-mixed object is 1.5-2.5；
Preferably, the pH value of the acid-mixed object is 1.5-2.
3. preparation method according to claim 1, which is characterized in that the temperature of first hydro-thermal reaction is 110-300
DEG C, the time is at least 8h；
Preferably, the temperature of second hydro-thermal reaction is the time 8-30h at 130 DEG C -250 DEG C.
4. preparation method according to claim 1, which is characterized in that the temperature of second hydro-thermal reaction is 110-300
DEG C, the time is at least 6h；
Preferably, the temperature of second hydro-thermal reaction is the time 6-20h at 130 DEG C -240 DEG C.
5. preparation method according to claim 1, which is characterized in that the calcining in the step 3) includes: with 10-70
DEG C/rate of h is warming up to 200-350 DEG C of holding at least 2h, 500-1000 DEG C of heat preservation is warming up to extremely with the rate of 50-150 DEG C/h
Few 2h；
Preferably, the calcining in the step 3) includes: to be warming up to 250-300 DEG C of holding 3-7h with the rate of 20-60 DEG C/h, with
The rate of 70-120 DEG C/h is warming up to 700-950 DEG C of heat preservation 3-8h.
6. preparation method according to claim 1, which is characterized in that the gas flow of the calcining in the step 3) is 5-
30L/min/kg oxide, the gas are selected from air or non-active gas；
Preferably, the air mass flow of the calcining in the step 3) is 10-20L/min/kg oxide.
7. preparation method according to claim 1, which is characterized in that the concentration of the oxide of the metal in the just mixed object
For 20-100g/L；
Preferably, the oxide concentration of the metal in the just mixed object is 30-80g/L.
8. preparation method according to claim 1, which is characterized in that the washing in the step 3) is to use organic solvent
Washing；
Preferably, the organic solvent is selected from least one of ether, pure and mild ketone.
9. preparation method according to claim 1, which is characterized in that include that addition is excessive before the filtering of the step 3)
The step of alkaline precipitating agent.
10. preparation method according to claim 1, which is characterized in that the cerium zirconium compound oxide includes 75-
The mass ratio of the cerium oxide and zirconium oxide of 100wt%, the cerium oxide and zirconium oxide is 0.25-0.9:1；
Preferably, the mass ratio of the cerium oxide and zirconium oxide is 0.3-0.8:1.
11. preparation method according to claim 1, which is characterized in that the alkaline precipitating agent is selected from ammonium hydroxide, hydroxide
At least one of sodium, potassium hydroxide and organic amine；
Preferably, the alkaline precipitating agent is ammonium hydroxide.
12. a kind of cerium zirconium compound oxide, which is characterized in that it is prepared by method of any of claims 1-11
To or, cerium zirconium compound oxide made from method of any of claims 1-11 through 500-1200 DEG C of calcining at least 1h
It is made.
13. cerium zirconium compound oxide described in claim 12 is preparing the application in catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110694621A (en) * | 2019-09-09 | 2020-01-17 | 山东国瓷功能材料股份有限公司 | Three-way catalyst and preparation method and application thereof |
| CN110841623A (en) * | 2019-10-12 | 2020-02-28 | 山东国瓷功能材料股份有限公司 | Cerium-zirconium composite oxide with stable high-temperature structure and preparation method thereof |
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| CN1552517A (en) * | 2003-12-19 | 2004-12-08 | 广东工业大学 | Preparation of nano cerium-zirconium rare-earth composite fluorine compound solid solution based catalyst |
| CN109465003A (en) * | 2018-10-09 | 2019-03-15 | 山东国瓷功能材料股份有限公司 | A kind of rare earth element composite oxides and its preparation method and application |
| CN109529801A (en) * | 2018-11-12 | 2019-03-29 | 山东国瓷功能材料股份有限公司 | Controllable double hole channel cerium zirconium compound oxide and its preparation method and application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1552517A (en) * | 2003-12-19 | 2004-12-08 | 广东工业大学 | Preparation of nano cerium-zirconium rare-earth composite fluorine compound solid solution based catalyst |
| CN109465003A (en) * | 2018-10-09 | 2019-03-15 | 山东国瓷功能材料股份有限公司 | A kind of rare earth element composite oxides and its preparation method and application |
| CN109529801A (en) * | 2018-11-12 | 2019-03-29 | 山东国瓷功能材料股份有限公司 | Controllable double hole channel cerium zirconium compound oxide and its preparation method and application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110694621A (en) * | 2019-09-09 | 2020-01-17 | 山东国瓷功能材料股份有限公司 | Three-way catalyst and preparation method and application thereof |
| CN110841623A (en) * | 2019-10-12 | 2020-02-28 | 山东国瓷功能材料股份有限公司 | Cerium-zirconium composite oxide with stable high-temperature structure and preparation method thereof |
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