CN101696034B - Method for preparing nano-cerium oxide and zirconia solid solution - Google Patents
Method for preparing nano-cerium oxide and zirconia solid solution Download PDFInfo
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Abstract
The invention discloses a method for preparing nano-cerium oxide and zirconia solid solutions, which belongs to the field of inorganic catalytic materials. The method comprises: dissolving cerium-containing ionic compound accounting for 10 to 90 percent of the weight of the raw materials and zirconium-containing ionic compound accounting for 10 to 90 percent of the weight of the raw materials in deionized water respectively according to a formulation of raw materials of nano-cerium oxide and zirconia solid solutions, and preparing the two into solutions with the concentration between 1 and 3 M; mixing the two solutions, adding alkaline substances, regulating pH between 7 and 10 to generate precipitate, aging the precipitate through heat treatment, performing washing and centrifugal filtration to obtain a filter cake; dissolving the obtained filter cake in nitric acid, adding surfactant to obtain milky white colloid; and performing calcination to prepare composite oxide of nano-cerium oxide/zirconia. Nano-sized particles prepared by the method improve the microstructure of cerium/zirconium solid solutions, and the prepared nano-composite oxide solid solutions have better thermal stability and larger specific surface area.
Description
Technical field:
The present invention relates to the preparation method of a kind of nano-cerium oxide and zirconia solid solution.This type of composite oxide solid solution can be used for cleaning catalyst for tail gases of automobiles and other catalytic material.
Technical background:
China's rare earth reserves account for the nearly 70% of world's total reserves, and rare earth reserves and output all occupy the first in the world.Nineteen ninety-five, the rare earth consumption was only second to the U.S., occupied the second in the world; From 2000, China's rare earth consumption surpassed the U.S., occupy the No. 1 in the world, and China's rare earth consumption accounted for 35% of global aggregate consumption in 2003.In the U.S., automobile catalyst is the maximum user of rare earths material, and rare earth application percentage in China's automotive catalysts is less.1996, the rare earth consumption of the U.S. in cleaning catalyst for tail gases of automobiles reaches 1.3 ten thousand tons (in REO-alkene soil oxide compounds), account for 46% of U.S.'s rare earth total flow then, more rose in 1999 and account for 60% of its aggregate consumption, China's automobile catalyst only accounts for the less than 2% of aggregate consumption, compares with application level with external application quantity to have a long way to go.
This shows, China native country automobile-use catalyzer enterprise on the one hand to the development and application demand of high-performance novel rare-earth material in the catalyzer in continuous increase; On the other hand because himself less share of market has limited with rare earth enterprise the optimum innovation that forms common exploitation, realizes doulbe-sides' victory.Therefore, when seeing that automotive catalysts is with rare earth material great market prospect, should unimpeded rare earth enterprise and the cooperation channel of automotive catalysts enterprise, form and have complementary advantages, improve fundamental research level and industrialization level and give full play to China's rare earth resources advantage, promote the development of rare earth based automotive catalysts green technology, promote China's rare-earth products to make the transition to high added value, diversification direction.China is as world's rare earth big country, and the development of automobile-use rare-earth products not only will more will be conceived to move towards the world market towards Chinese market.
Along with the motor vehicle exhaust rules are more and more stricter, it is more and more important to be used to the catalytic conversion technique handled with the cleaning atmospheric pollution thing.The core material that this type of catalyzed conversion usually adopts catalyzer to transform as pollutent.Along with the raising gradually of catalytic performance, adopt rare earth oxide and composite oxides thereof to improve activity of such catalysts, stability and selectivity and seem very important as catalytic material.For example auto-exhaust catalyst (three-way catalyst) adopts cerium zirconium compound oxide to improve the oxygen storage capacity of catalyzer, thereby improves the activity that the catalyzer that contains precious metal transforms carbon monoxide, oxynitride and hydrocarbon polymer.Because precious metal costs an arm and a leg, thereby increase economic efficiency, reduce the consumption of precious metal, and keep good three-effect catalysis activity simultaneously, also have high low temperature active and high thermostability simultaneously, become the target that the brainstrust of research purifying vehicle exhaust technology lays siege to.
Chinese invention patent 02110041.1 discloses a kind of preparation technology based on cerium oxide and zirconic composite oxide solid solution, its composite oxides comprise cerium oxide 10～90% (wt), zirconium white 10～90% (wt), it is characterized in that it being to be mixed in proportion through alkali precipitation, throw out thermal treatment, oven dry, calcining are made by the solution that contains cerium ion and zirconium ion.This method is simple to operate, and technological process is easy to control, is a kind of not only economy but also the method for preparing oxide catalyst that is easy to suitability for industrialized production.This preparation method uses coprecipitation method more widely at present, but also has some shortcomings, easily influences product purity as the precipitation agent that adds, and the different metal ion precipitation is inhomogeneous, and the particulate agglomeration traits solves with can not get, less stable or the like.
People such as Nunan John G adopt traditional sol-gel method, make CeO by adding citric acid complexing agent
2-ZrO
2Solid solution, the add-on of water has a significant effect to its performance when pH value, gelation temperature and hydrolysis.Also there are some problems in this method, and as owing to use alkoxide as raw material, the cost height has pollution in heat treatment process, because its specific surface is big, easily hardens, and whole sol-gel process required time is longer.
Summary of the invention:
Technical problem to be solved by this invention provides a kind of preparation method based on nano-cerium oxide and zirconia solid solution, improve further that particulate is reunited, the distribution of stablizer, thing mutually and suppress growing up and sintering of crystal grain, obtain good stability, nano cerium zirconium sosoloid that specific surface area is big.
The object of the invention is achieved through the following technical solutions:
The preparation method of a kind of nano-cerium oxide and zirconia solid solution may further comprise the steps and processing condition:
(1),, all is configured to the solution of concentration 1～3M with accounting for containing the cerium ion compound and account for raw material weight 10～90% and containing the zirconium ion compound and be dissolved in deionized water respectively of raw material weight 10～90% according to the prescription of nano-cerium oxide and zirconia solid solution raw material; To add alkaline matter after this two solution mixing, regulating the pH value is 7～10, generates precipitation, and precipitation is washed through the thermal treatment ageing, and centrifuging obtains filter cake; The described cerium ion compound that contains is cerous nitrate or cerous sulfate; The described zirconium ion compound that contains is a Zircosol ZN, propyl alcohol zirconium or butanols zirconium; Described alkaline matter is an ammoniacal liquor; Described raw material is for containing the cerium ion compound and containing the zirconium ion compound;
(2) step (1) gained filter cake is dissolved in the nitric acid, adds tensio-active agent, its consumption is the following 15～25h of backflow of 0.1%～0.5%, 100 ℃～150 ℃ of cerium zirconium compound oxide weight, gets the oyster white colloid; Described tensio-active agent is Sodium dodecylbenzene sulfonate or cetyl trimethylammonium bromide;
(3) with after the colloid drying in retort furnace 400～900 ℃ the calcining 3～5h, obtain prepared nano-cerium oxide and zirconic composite oxides.
For further realizing the object of the invention, described ammonia concn is preferably 0.1～6.0mol/L.
Described concentration of nitric acid is preferably 0.1～10.0mol/L.
Described precipitation temperature is preferably room temperature～100 ℃.
Described thermal treatment ageing is to stir under 100 ℃～300 ℃ temperature, and the time is 0.5～24 hour, obtains the stable white precipitation.
Adopt the composite oxide solid solution of the nano cerium zirconium that the present invention obtains to be used for the preparation of multiple catalytic material, can adopt the material of this product of the present invention as cleaning catalyst for tail gases of automobiles, catalytic incineration catalyst, water-gas shift reaction catalyst, ethanol hydrogen production catalyzer, catalyst for phenylethylene dehydrogenation, selective oxidation catalyzer, oxy-dehydrogenation catalyst and other.
With respect to prior art, the present invention has following advantage:
(1) the present invention adopts the improvement sol-gel method successfully to prepare the nano particle cerium zirconium sosoloid.Raw materials used being dispersed in of this method forms low viscous gel in the solvent, can obtain the homogeneity on the molecular level in a short period of time, can quantitatively mix other elements, realizes the accurate doping on the molecular level.
(2) the present invention can prepare purity height, size distribution is even, chemically reactive is high single, multicomponent mixture (molecular level mixing) at low temperatures, and can prepare the product that traditional method can not or be difficult to prepare, be particularly useful for making amorphous material or nano material.
(3) experimental result XRD goes out the peak position at 29.6 °, and 34.0 °, 48.9 °, 58.1 °, show and have only single crystalline phase cube phase, show that the oxide compound that the present invention obtains exists with purified sosoloid phase form.
(4) gained nano-cerium oxide of the present invention and zirconia solid solution have can cleaning of off-gas in the effect of CO and HC, simultaneously again can cleaning of off-gas in NO
XEffect, can be used as novel three-effect catalysis agent material;
(5) gained nano-cerium oxide of the present invention and zirconia solid solution thermostability height, but the sintering of catalytic material does not take place in below 900 ℃ in steady operation.
Description of drawings:
Fig. 1 is the nano particle cerium zirconium sosoloid oxide compound with the Prepared by Sol Gel Method different ratios, calcines the XRD spectra that obtained in 3 hours down at 450 ℃.
Fig. 2 is the SEM figure of the nano cerium zirconium sosoloid of example 1 preparation.
Fig. 3 is the SEM figure of the nano cerium zirconium sosoloid of example 2 preparations.
Fig. 4 is the SEM figure of the nano cerium zirconium sosoloid of example 3 preparations.
Fig. 5 is the SEM figure of the nano cerium zirconium sosoloid of example 4 preparations.
Fig. 6 is the SEM figure of the nano cerium zirconium sosoloid of example 5 preparations.
Fig. 7 is the SEM figure of the nano cerium zirconium sosoloid of comparative example 1 preparation.
Embodiment:
The present invention will be further described below in conjunction with example and accompanying drawing, but embodiments of the present invention are not limited thereto.
Embodiment 1:
Adopt sol-gel method: the cerium source is cerous nitrate Ce (NO in the raw material
3)
36H
2O, the zirconium source is ZrO (NO
3)
22H
2O.Tensio-active agent is a Sodium dodecylbenzene sulfonate.Add the zirconyl nitrate solution of 0.1mol/L concentration in the cerous nitrate solution of 0.1mol/L concentration, cerous nitrate and Zircosol ZN molar ratio are 1: 3.Add the ammoniacal liquor of 1mol/L concentration in the mixture of two kinds of solution, regulating the pH value is 9, then solution is adjusted to 120 ℃ and kept 6 hours.Washing repeatedly obtains the purified hydrogen oxide precipitation after filtration, and precipitation is heat-treated ageing, and post precipitation obtains the deposit seeds of complete crystal formation through thermal treatment, precipitate more complete, stablize.120 ℃ of the temperature of handling, 6 hours time.Then with resolution of precipitate in 1mol/L nitric acid, cerium zirconium compound oxide concentration sum is adjusted to 35g/L, and adding the tensio-active agent Sodium dodecylbenzene sulfonate, its add-on is 0.5% of a cerium zirconium compound oxide weight, and transfers in the there-necked flask and refluxed 20 hours down at 100 ℃.Centrifugal through whizzer, drying was calcined 3 hours down at 450 ℃ then.
The cerium Zirconium oxide was calcined 12 hours down at 800 ℃ and 1000 ℃ respectively, and the specific surface area of the oxide compound after wearing out is respectively 72m
2/ g and 45m
2/ g.This shows, better by the cerium zirconium sosoloid stability that this method makes, after high-temperature calcination is aging, still have bigger specific surface area.
SEM figure shows the granular size situation of prepared product, and as shown in Figure 2, the cerium zirconium sosoloid particle by this method preparation has obtained good dispersion, and maximum particle has 209nm, and minimum have only 69nm.Particle size dispersion is more even, and most of granular size is below 100nm.
Embodiment 2:
Adopt sol-gel method: the cerium source is cerous nitrate Ce (NO
3)
36H
2O, the zirconium source is ZrO (NO
3)
22H
2O, tensio-active agent are Sodium dodecylbenzene sulfonate, add the 0.1mol/L zirconyl nitrate solution in the 1mol/L cerous nitrate solution, and the molar ratio of cerous nitrate and Zircosol ZN is 1: 1.Add 0.1mol/L ammoniacal liquor in the mixture of two kinds of solution, regulating the pH value is 10, then solution is adjusted to 120 ℃ and kept 6 hours.Washing repeatedly obtains the purified hydrogen oxide precipitation after filtration, and precipitation is heat-treated, 100 ℃ of the temperature of processing, 0.5 hour time.Then with resolution of precipitate in 0.1mol/L nitric acid, cerium zirconium compound oxide concentration sum is adjusted to 35g/L, and adding the tensio-active agent Sodium dodecylbenzene sulfonate, its add-on is 0.5% of a cerium zirconium compound oxide weight, and transfers in the there-necked flask and refluxed 25 hours down at 150 ℃.Centrifugal through whizzer, drying was calcined 3 hours down at 450 ℃ then.
The cerium Zirconium oxide was calcined 12 hours down at 800 ℃ and 1000 ℃ respectively, and the specific surface area of the oxide compound after wearing out is respectively 65m
2/ g and 39m
2/ g.This shows that the cerium zirconium sosoloid that makes by this method is along with the increase of the content of cerium, specific surface area decreases, but stability is still better, after high-temperature calcination is aging, still has certain specific surface area.
SEM figure shows the granular size situation of prepared product, and as shown in Figure 3, the cerium zirconium sosoloid particle for preparing by this method has obtained good dispersion, and particle size dispersion is more even, and most of granular size is below 100nm.
Embodiment 3:
Adopt sol-gel method: the cerium source is cerous nitrate Ce (NO
3)
36H
2O, the zirconium source is ZrO (NO
3)
22H
2O, tensio-active agent are Sodium dodecylbenzene sulfonate, add the 1mol/L zirconyl nitrate solution in the 0.1mol/L cerous nitrate solution, and the molar ratio of cerous nitrate and Zircosol ZN is 3: 1.Add 1mol/L ammoniacal liquor in the mixture of two kinds of solution, regulating the pH value is 9, then solution is adjusted to 120 ℃ and kept 6 hours.Washing repeatedly obtains the purified hydrogen oxide precipitation after filtration, and precipitation is heat-treated, 300 ℃ of the temperature of processing, 24 hours time.Then with resolution of precipitate in 1mol/L nitric acid, cerium zirconium compound oxide concentration sum is adjusted to 35g/L, and adding the tensio-active agent Sodium dodecylbenzene sulfonate, its add-on is 0.5% of a cerium zirconium compound oxide weight, and transfers in the there-necked flask and refluxed 20 hours down at 100 ℃.Centrifugal through whizzer, drying was calcined 3 hours down at 450 ℃ then.
The cerium Zirconium oxide was calcined 12 hours down at 800 ℃ and 1000 ℃ respectively, and the specific surface area of the oxide compound after wearing out is respectively 62m
2/ g and 42m
2/ g.This shows, better by the cerium zirconium sosoloid stability that this method makes, after high-temperature calcination is aging, still have certain specific surface area.
Be illustrated in figure 1 as the cerium zirconium compound oxide that three kinds of different proportionings obtain, the X-ray diffraction analysis revealed is as Ce/Zr=1: 1 or 1: 3 the time, not only contain cubic crystalline phase but also contain a cube crystalline phase in the gained composite oxides, have only as Ce/Zr=3: in the time of 1, it goes out the peak position at 29.6 °, 34.0 °, 48.9 °, 58.1 °, show and have only single crystalline phase cube phase, show that the oxide compound that is only obtained just exists with purified sosoloid phase form under this proportioning.
SEM figure shows the granular size situation of prepared product, and as shown in Figure 4, the cerium zirconium sosoloid particle for preparing by this method has obtained good dispersion, and particle size dispersion is more even, and most of granular size is below 100nm.
Embodiment 4:
Adopt sol-gel method: the cerium source is cerous sulfate Ce (SO in the raw material
4) 8H
2O, the zirconium source is Zr (OC
4H
9)
4, tensio-active agent is a cetyl trimethylammonium bromide.Add the 0.1mol/L zirconyl nitrate solution in the 0.1mol/L cerous nitrate solution, cerous nitrate and Zircosol ZN molar ratio are 3: 1.Add 1mol/L ammoniacal liquor in the mixture of two kinds of solution, regulating the pH value is 9, and solution is adjusted to 120 ℃ and kept 6 hours then.Washing repeatedly obtains the purified hydrogen oxide precipitation after filtration, and precipitation is heat-treated, 120 ℃ of the temperature of processing, 6 hours time.Then with resolution of precipitate in 10mol/L nitric acid, cerium zirconium compound oxide concentration sum is adjusted to 35g/L, and adding the tensio-active agent Sodium dodecylbenzene sulfonate, its add-on is 0.5% of a cerium zirconium compound oxide weight, and transfers in the there-necked flask and refluxed 20 hours down at 100 ℃.Centrifugal through whizzer, drying was calcined 3 hours down at 450 ℃ then, obtained the cerium Zirconium oxide.The cerium Zirconium oxide was calcined 12 hours down at 800 ℃ and 1000 ℃ respectively, and the specific surface area of the oxide compound after wearing out is respectively 58m
2/ g and 43m
2/ g.
SEM figure shows the granular size situation of prepared product, and as shown in Figure 5, the cerium zirconium sosoloid particle for preparing by this method has obtained good dispersion, and particle size dispersion is more even, but particle is bigger.
Embodiment 5:
Adopt sol-gel method: the cerium source is cerous sulfate Ce (SO in the raw material
4) 8H
2O, the zirconium source is Zr (OC
2H
5)
4, tensio-active agent is a cetyl trimethylammonium bromide.Add the 0.1mol/L zirconyl nitrate solution in the 0.1mol/L cerous nitrate solution, cerous nitrate and Zircosol ZN molar ratio are 3: 1.Add 1mol/L ammoniacal liquor in the mixture of two kinds of solution, regulating the pH value is 9, and solution is adjusted to 120 ℃ and kept 6 hours then.Washing repeatedly obtains the purified hydrogen oxide precipitation after filtration, and precipitation is heat-treated, 120 ℃ of the temperature of processing, 6 hours time.Then with resolution of precipitate in 1mol/L nitric acid, cerium zirconium compound oxide concentration sum is adjusted to 35g/L, and adding the tensio-active agent Sodium dodecylbenzene sulfonate, its add-on is 0.5% of a cerium zirconium compound oxide weight, and transfers in the there-necked flask and refluxed 20 hours down at 100 ℃.Centrifugal through whizzer, drying was calcined 3 hours down at 450 ℃ then, obtained the cerium Zirconium oxide.The cerium Zirconium oxide was calcined 12 hours down at 800 ℃ and 1000 ℃ respectively, and the specific surface area of the oxide compound after wearing out is respectively 61m
2/ g and 38m
2/ g.
SEM figure shows the granular size situation of prepared product, and as shown in Figure 6, particle has agglomeration to take place, and this may be that the zirconium source is not suitable for preparing the nanometer solid solution pellet owing to the cerium source of adopting.
Comparative example 1:
Adopt coprecipitation method: add the 0.1mol/L zirconyl nitrate solution in the 0.1mol/L cerous nitrate solution, the molar ratio by oxide compound is 3: 1 separately.Add 1mol/L ammoniacal liquor in the mixture of two kinds of solution, regulating the pH value is 9, and cerium zirconium compound oxide concentration sum is adjusted to 35g/L.Washing obtains the purified hydrogen oxide precipitation after filtration.Precipitation is heat-treated, 120 ℃ of the temperature of processing, 6 hours time.
The precipitation of hydroxide that obtains was calcined 3 hours down at 450 ℃.
Calcined 12 hours down at 800 ℃ and 1000 ℃, the specific surface area of the oxide compound after wearing out is respectively 31m
2/ g and 26m
2/ g.The nano composite oxide less stable that explanation prepares with this method.Behind long-time high temperature ageing, specific surface area has bigger decline.
As shown in Figure 7, SEM figure shows that more serious agglomeration has taken place the prepared product of employing coprecipitation method, and specific surface area reduces, and catalytic performance reduces, and the serious phenomenon that hardens takes place.
All examples listed by table 1 and comparative example was calcined 12 hours the specific surface area data of the oxide compound after wearing out down through 800 ℃ and 1000 ℃.Can obviously find out, adopt the cerium zirconium sosoloid of Prepared by Sol Gel Method of the present invention, through behind the high temperature ageing, specific surface area is obviously greater than the specific surface area of the cerium zirconium sosoloid that adopts the coprecipitation method preparation.
Table 1 is analyzed numerical value and measurement result
| The specific surface area of 800 ℃ of calcinings after 12 hours | 12 hours specific surface area of 1000 ℃ of calcinings | |
| Embodiment 1 | 72m 2/g | 45m 2/g |
| Embodiment 2 | 65m 2/g | 39m 2/g |
| Embodiment 3 | 62m 2/g | 42m
2/ |
| Embodiment | ||
| 4 | 58m 2/g | 43m 2/g |
| Embodiment 5 | 61m 2/g | 38m 2/g |
| Comparative Examples 1 | 31m 2/g | 26m 2/g |
Claims (5)
1. the preparation method of nano-cerium oxide and zirconia solid solution is characterized in that may further comprise the steps and processing condition:
(1),, all is configured to the solution of concentration 1～3M with accounting for containing the cerium ion compound and account for raw material weight 10～90% and containing the zirconium ion compound and be dissolved in deionized water respectively of raw material weight 10～90% according to the prescription of nano-cerium oxide and zirconia solid solution raw material; To add alkaline matter after this two solution mixing, regulating the pH value is 7～10, generates precipitation, and precipitation is washed through the thermal treatment ageing, and centrifuging obtains filter cake; The described cerium ion compound that contains is cerous nitrate or cerous sulfate; The described zirconium ion compound that contains is a Zircosol ZN, propyl alcohol zirconium or butanols zirconium; Described alkaline matter is an ammoniacal liquor; Described raw material is for containing the cerium ion compound and containing the zirconium ion compound;
(2) step (1) gained filter cake is dissolved in the nitric acid, adds tensio-active agent, its consumption is the following 15～25h of backflow of 0.1%～0.5%, 100 ℃～150 ℃ of cerium zirconium compound oxide weight, gets the oyster white colloid; Described tensio-active agent is Sodium dodecylbenzene sulfonate or cetyl trimethylammonium bromide;
(3) with after the colloid drying in retort furnace 400～900 ℃ the calcining 3～5h, obtain prepared nano-cerium oxide and zirconic composite oxides.
2. the preparation method of nano-cerium oxide according to claim 1 and zirconia solid solution, its feature exists: described ammonia concn is 0.1～6.0mol/L.
3. the preparation method of nano-cerium oxide according to claim 1 and zirconia solid solution, its feature exists: described concentration of nitric acid is 0.1～10.0mol/L.
4. the preparation method of nano-cerium oxide according to claim 1 and zirconia solid solution, its feature exists: described precipitation temperature is room temperature～100 ℃.
5. the preparation method of nano-cerium oxide according to claim 1 and zirconia solid solution, its feature exists: described thermal treatment ageing is to stir under 100 ℃～300 ℃ temperature, and the time is 0.5～24 hour, obtains the stable white precipitation.
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