CN114433061B - Preparation method of nano cerium-zirconium solid solution and nano cerium-zirconium solid solution prepared by same - Google Patents
Preparation method of nano cerium-zirconium solid solution and nano cerium-zirconium solid solution prepared by same Download PDFInfo
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- 239000006104 solid solution Substances 0.000 title claims abstract description 68
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002002 slurry Substances 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 24
- 238000001694 spray drying Methods 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 19
- 239000000839 emulsion Substances 0.000 claims abstract description 18
- 150000000703 Cerium Chemical class 0.000 claims abstract description 16
- 150000003754 zirconium Chemical class 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 15
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 14
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical group [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229960001759 cerium oxalate Drugs 0.000 claims description 3
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 description 31
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000000919 ceramic Substances 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000002776 aggregation Effects 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 229910000420 cerium oxide Inorganic materials 0.000 description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 238000005054 agglomeration Methods 0.000 description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000011812 mixed powder Substances 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- 238000009827 uniform distribution Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- -1 rare earth carbonate Chemical class 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of a nano cerium-zirconium solid solution, which comprises the following steps: s1, preparing slurry; s2, adding water into the slurry, performing ball milling, and passing through a 80-mesh filter screen to obtain uniform emulsion/suspension; s3, dripping the emulsion/suspension obtained in the step S2 into drying equipment under the stirring state for spray drying, and obtaining dry powder with the water content not higher than 20wt%; and S4, calcining the dried powder obtained in the step S3 in a furnace body, and cooling to room temperature after calcining to obtain the nano cerium-zirconium solid solution. The invention takes insoluble cerium salt and insoluble zirconium salt as raw materials, and can obtain the nano cerium-zirconium solid solution with small granularity and uniform granularity distribution. The invention also provides a nano cerium-zirconium solid solution.
Description
Technical Field
The invention relates to the field of material preparation, and in particular provides a preparation method of a nano cerium-zirconium solid solution. The invention also provides a nano cerium-zirconium solid solution.
Background
With the rapid development of the automobile industry, automobile exhaust pollution has attracted general social interest, and the catalytic purification of automobile exhaust by using a three-way catalyst (TWC) is one of the main ways to solve the exhaust pollution at present. Since the beginning of the 80 s of the last century, cerium oxide-based high-performance rare earth oxygen storage materials are widely applied to three-effect catalysts for purifying automobile exhaust, become key materials of the three-effect catalysts, determine the performance and service life of the catalysts, and are the focus of competition of various enterprises in the field of automobile exhaust purification catalysts. Because of the poor aging resistance of pure cerium oxide, the oxygen storage capacity is substantially lost when the firing temperature is higher than 850 ℃. The research result shows that adding proper amount of zirconium into cerium oxide can raise the heat stability and oxygen storing performance of cerium oxide obviously, and the cerium-zirconium solid solution becomes the second generation oxygen storing material for automobile tail gas purifying catalyst. Although the oxygen storage performance and the aging resistance of the cerium-zirconium solid solution are obviously superior to those of pure cerium oxide, the high oxygen storage amount can be maintained even when obvious sintering occurs at high temperature, the performance of the three-way catalyst for purifying automobile exhaust, particularly the thermal stability and the oxygen storage performance of the oxygen storage material, still need to be further improved along with the continuous increase of the storage amount of automobiles and the increasing severity of environmental pollution.
The existing methods for preparing the cerium-zirconium solid solution mainly comprise a coprecipitation method, a sol-gel method, a microemulsion method, a hydrothermal method, a high-energy ball milling method and the like. The co-precipitation method has the advantages of simple process, easy control of conditions, good product uniformity, low production cost, convenient industrial production and the like, but the conventional co-precipitation method has various processes, and the prepared cerium-zirconium solid solution performance cannot meet the requirements of automobile exhaust gas purification catalysts in certain aspects, such as oxygen storage amount and thermal stability or specific surface area, and is difficult to meet by coworkers.
At present, the main method for preparing the cerium-zirconium solid solution is a soluble salt precipitation method, for example, the patent application No. CN201910149653.9 discloses a preparation method of a nano cerium-zirconium solid solution, and specifically discloses a preparation method of a cerium-zirconium solid solution with large specific surface area, good oxygen storage performance and thermal stability, which is prepared by adding glycol and polyethylene glycol into an aqueous solution of cerium nitrate and zirconyl chloride, adding a surfactant, naCl and a complexing agent, heating to 100 ℃, adding ammonia water to regulate pH to 8-9, precipitating for 8 hours, and finally centrifuging, washing, drying and calcining. The acid radical ions brought by a large amount of soluble salts can generate great environmental protection problem, and the investment in environmental protection is increased, so that the production cost is increased, and the particle size of particles is obviously increased when the nano oxide is calcined, so that the nano oxide becomes submicron oxide; the invention patent application with the application number of CN201610235053.0 discloses a preparation method of a nano cerium-zirconium solid solution, and in particular discloses a preparation method of a nano cerium-zirconium solid solution, wherein cerium carbonate, zirconium carbonate and doped rare earth carbonate are respectively dissolved in concentrated nitric acid to obtain cerium nitrate solution, zirconium nitrate solution and doped rare earth nitrate solution, the cerium nitrate solution, the zirconium nitrate solution and the doped rare earth nitrate solution are prepared into a mixed salt solution, and hydrogen peroxide is added; adding a surfactant into the solution prepared by the precipitant, and dividing the solution into at least two parts; dropwise adding the mixed salt solution into the precipitant solution by a pH swing precipitation method; finally, aging, washing, roasting and sieving the precipitate by a pair of rollers to obtain the cerium-zirconium solid solution. Said invention also can greatly raise cost, and at the same time can produce a certain effect on product purity, and when the nano oxide is calcined, the grain size of the grain is obviously grown so as to obtain the invented submicron oxide.
Titration of the precipitant into the cerium-zirconium salt solution in the existing precipitation method technology can lead to uneven concentration of a reaction system, so that the growth speed of cerium-zirconium ions is difficult to control, and the prepared cerium-zirconium solid solution powder is easy to have wide particle size distribution range and large particle size; in addition, the preparation method has complicated steps and equipment, various variables are required to be controlled, the particle size distribution range of the powder is not adjustable, the agglomeration phenomenon of the nano cerium-zirconium solid solution prepared by a hydrothermal method is serious, and the separation is difficult.
Disclosure of Invention
In order to solve the problems of purity of products and easy environmental pollution in the prior art, the invention provides a preparation method of a nano cerium zirconium solid solution and the nano cerium zirconium solid solution prepared by the method, and provides a method for preparing nano cerium zirconium solid solution powder by taking insoluble cerium salt and insoluble zirconium salt as raw materials and adding melting assisting salt and adopting a simple high-temperature calcination process means. Is easy for industrialized production.
The preparation method of the nano cerium-zirconium solid solution comprises the following steps:
S1, preparing slurry: uniformly mixing cerium salt and zirconium salt which are insoluble in water and have the mass ratio of 1:0.1-10 to obtain mixed salt; adding molten salt into water, stirring until the molten salt is dissolved, adding a dispersing agent and a surfactant, and mixing to obtain a mixed solution; gradually adding the mixed solution into the mixed salt, and mechanically stirring until the mixed solution is uniformly dispersed to obtain the required slurry; wherein the mass ratio of the mixed salt to the molten salt is 1:0.01-5, and the mass ratio of the mixed salt to the water is 1:0.1-5;
S2, adding water into the slurry, performing ball milling, and passing through a 80-mesh filter screen to obtain uniform emulsion/suspension; wherein the mass ratio of the slurry to the water is 0.5-4: 1, a step of;
s3, dripping the emulsion/suspension obtained in the step S2 into drying equipment under the stirring state for spray drying, and obtaining dry powder with the water content not higher than 20wt%;
S4, calcining the dried powder obtained in the step S3 in a furnace body, wherein the calcining stage comprises the following steps: the temperature rise rate is 0.1-50 ℃/min from room temperature to 400 ℃, the temperature rise rate is 0.1-50 ℃/min from 400-600 ℃, the temperature rise rate is 600-900 ℃, the temperature rise rate is 0.1-50 ℃/min, and the heat preservation time of the highest temperature is 30-90 min; and cooling to room temperature after calcination to obtain the nano cerium zirconium solid solution.
Further, the dispersing agent in the step S1 is polyethylene glycol.
Further, the surfactant in step S1 is one or more of cetyltrimethylammonium bromide, polyethylene glycol, stearic acid and quaternary ammonium compound.
Further, in step S1, the cerium salt in the mixed salt is cerium carbonate or cerium oxalate, and the zirconium salt is zirconium carbonate.
Further, in step S1, the molten salt is ammonium chloride or sodium chloride.
In step S2, the ball milling time is 5-10 min.
Further, in step S3, the spray drying temperature is 100 to 200 ℃.
The invention also provides a nano cerium zirconium solid solution which is prepared by the preparation method of the nano cerium zirconium solid solution.
The beneficial effects are that:
1. The invention adopts insoluble salts such as cerium carbonate, cerium oxalate and the like as main raw materials and adopts a special calcination technology, thereby obtaining cerium oxide particles with the minimum 30 nanometers, and the cerium oxide particles have the advantages of uniform particle size, good dispersibility, high calcination temperature and complete crystal form growth.
2. The preparation method of the nano cerium-zirconium solid solution is simple and stable, has few procedures, low requirements on equipment, few raw material types, and low production cost, and generates tail gas which is easy to absorb and treat, and is nontoxic and pollution-free; in addition, by adding polyethylene glycol and a certain amount of surfactant, the produced nano cerium-zirconium solid solution is spherical, has high purity, no agglomeration, narrow particle size distribution and easy dispersion.
Detailed Description
In the following, a technical solution in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art without making any inventive effort, are intended to be within the scope of the present invention.
Example 1
The embodiment provides a preparation method of a nano cerium-zirconium solid solution, which comprises the following steps:
S1, preparing slurry: uniformly mixing cerium salt and zirconium salt which are insoluble in water and have the mass ratio of 1:0.1-10 to obtain mixed salt; adding molten salt into water, stirring until the molten salt is dissolved, adding a dispersing agent and a surfactant, and mixing to obtain a mixed solution; gradually adding the mixed solution into the mixed salt, and mechanically stirring until the mixed solution is uniformly dispersed to obtain the required slurry; wherein the mass ratio of the mixed salt to the molten salt is 1:0.01-5, and the mass ratio of the mixed salt to the water is 1:0.1-5;
S2, adding water into the slurry, performing ball milling, and passing through a 80-mesh filter screen to obtain uniform emulsion/suspension; wherein the mass ratio of the slurry to the water is 0.5-4: 1, a step of;
s3, dripping the emulsion/suspension obtained in the step S2 into drying equipment under the stirring state for spray drying, and obtaining dry powder with the water content not higher than 20wt%;
S4, calcining the dried powder obtained in the step S3 in a furnace body, wherein the calcining stage comprises the following steps: the temperature rise rate is 0.1-50 ℃/min from room temperature to 400 ℃, the temperature rise rate is 0.1-50 ℃/min from 400-600 ℃, the temperature rise rate is 600-900 ℃, the temperature rise rate is 0.1-50 ℃/min, and the heat preservation time of the highest temperature is 30-90 min; and cooling to room temperature after calcination to obtain the nano cerium zirconium solid solution.
In this embodiment, the mass of the dispersant and the surfactant respectively accounts for one thousandth to ten thousandths of the solid mass of the raw material, and as a preferred embodiment, the mass of the dispersant and the surfactant respectively accounts for three thousandths of the solid mass of the raw material.
In this embodiment, the mechanical stirring and dispersing manner used in the step S1 is mechanical stirring at room temperature, and the mechanical stirring and dispersing effect is that the two water-insoluble cerium salts and zirconium salts are uniformly mixed, and the molten salt is fully mixed and dispersed with the two water-insoluble cerium salts and zirconium salts, so that the molten salt is adsorbed on the surfaces of the two water-insoluble cerium salts and zirconium salts;
the ball milling time in the step S2 is 5-10 min; the ball milling function is as follows: the two water-insoluble cerium salts and the zirconium salt are fully and uniformly mixed, and the molten salt is more uniformly and comprehensively adsorbed on the surfaces of the two water-insoluble cerium salts and the zirconium salt; because the cerium salt and the zirconium salt which are insoluble in water are dissociated under the action of mechanical force, free electrovalence bonds are generated on the new section, so that particle molecules are mutually aggregated, and the result is that the aggregation of the particles after calcination is more serious, but the acceleration combination of cerium salt particle molecules and zirconium salt particle molecules is accelerated, positive and negative ions generated by dissociation of a molten salt solution in an aqueous solution can be adsorbed on the surface of a ball milling product, and the aggregation phenomenon of the particles can be effectively inhibited;
The spray drying temperature in the step S3 is 100-200 ℃, and spray drying is adopted to refine and uniformly refine the precursor, so that the molten salt can be more uniformly and effectively adsorbed on the surfaces of two water-insoluble cerium salts and zirconium salts;
In the step S4, the crystallization of the nano cerium-zirconium solid solution is promoted by the high and low calcining temperatures, the time for rising to the maximum temperature and the heat preservation time of the maximum temperature, and the grain size of the nano cerium-zirconium solid solution can be controlled, wherein the heat preservation time of the maximum temperature is 30-90 min, and the calcining process can be specifically divided into: the preheating process activates the precursor, especially molten salt, from room temperature to 400 ℃ at a heating rate of 0.1-50 ℃/min and a heating time of 0-90 min, and part of molten salt begins to dissolve or decompose; the temperature rising rate is between 400 and 600 ℃, the temperature rising time is between 0.1 and 50 ℃/min, the temperature rising time is between 0 and 90min, the molten salt accelerates the decomposition kinetic rate of two water-insoluble cerium salts and zirconium salts, promotes the crystallization of oxides and the doping of zirconium element in cerium oxide crystal lattices to form cerium-zirconium solid solution, the decomposition of the molten salt at high temperature can break partial agglomeration or precursor with agglomeration trend or cerium-zirconium solid solution to a certain extent, the growth and agglomeration of cerium-zirconium solid solution crystal nuclei are effectively prevented, and the molten salt also maintains the dispersion function of particles of the cerium-zirconium solid solution by a grinding aid mechanism; the temperature rise rate is 0.1-50 ℃/min, the temperature rise time is 0-90 min, the time period aims at the rapid formation of the product cerium-zirconium solid solution crystal nucleus and the growth of crystal grains, the high temperature enables the product cerium-zirconium solid solution crystal nucleus to be rapidly formed, the existence of molten salt effectively prevents the growth and agglomeration of the cerium-zirconium solid solution crystal nucleus, and the particle size of the particles is controlled to a certain extent; finally cooling along with the furnace body or then rapidly cooling to obtain the nano cerium-zirconium solid solution; the furnace body used for calcination is a muffle furnace, a tube furnace, a gyratory furnace, a crucible resistance furnace, a box furnace, a lifting furnace, a pit furnace, a trolley furnace, a mesh belt furnace, a roller kiln, a pusher kiln, a tunnel furnace, a rotary kiln, a suspension calciner or the like calcination equipment with atmosphere.
The invention also provides a nano cerium zirconium solid solution which is prepared by the preparation method of the nano cerium zirconium solid solution.
Example 2
In the embodiment, 20g of cerium carbonate and 5g of zirconium carbonate are uniformly mixed, 1.75g of ammonium chloride is uniformly dissolved in 7.5g of deionized water at 90 ℃, 0.025g of polyethylene glycol and 0.025g of cetyltrimethylammonium bromide are added, the mixture is slowly poured into 25g of mixed powder of cerium carbonate and zirconium carbonate while stirring to obtain slurry, the slurry and a certain amount of deionized water are put into a ball mill to be ball-milled for 8min at a rotating speed of about 400r/min, the ball-milled slurry is filtered by a 80-mesh filter screen and is washed and sieved by a proper amount of deionized water, and the mass fraction of the obtained emulsion/suspension is controlled to be 40%; then stirring and spray-drying the emulsion/suspension, controlling the spray-drying temperature to be 115 ℃ and the feeding amount to be 550ml/h to obtain a mixture dry powder, wherein the water content of the powder after spray-drying is not higher than 20wt%; then placing the mixture powder into a ceramic crucible, placing the ceramic crucible into a muffle furnace, and setting the heating range as follows: the temperature is between room temperature and 800 ℃ and the heating time is 90min; the temperature keeping time at 800 ℃ is 60min. Cooling to room temperature along with the furnace for 40min to obtain the nano cerium-zirconium solid solution with the particle diameter of about 30nm and uniform distribution.
Example 3
In the embodiment, 20g of cerium carbonate and 5g of zirconium carbonate are uniformly mixed, 1.75g of ammonium chloride is uniformly dissolved in 7.5g of deionized water at 90 ℃, 0.025g of polyethylene glycol and 0.025g of cetyltrimethylammonium bromide are added, the mixture is slowly poured into 25g of mixed powder of cerium carbonate and zirconium carbonate while stirring to obtain slurry, the slurry and a certain amount of deionized water are put into a ball mill to be ball-milled for 8min at a rotating speed of about 400r/min, the ball-milled slurry is filtered by a 80-mesh filter screen and is washed and sieved by a proper amount of deionized water, and the mass fraction of the obtained emulsion/suspension is controlled to be 40%; then stirring and spray-drying the emulsion/suspension, controlling the spray-drying temperature to be 115 ℃ and the feeding amount to be 550ml/h to obtain a mixture dry powder, wherein the water content of the powder after spray-drying is not higher than 20wt%; then placing the mixture powder into a ceramic crucible, placing the ceramic crucible into a muffle furnace, and setting the heating range as follows: the temperature is between room temperature and 800 ℃ and the heating time is 60 minutes; the temperature keeping time at 800 ℃ is 90min. Cooling to room temperature along with the furnace for 40min to obtain the nano cerium-zirconium solid solution with the particle diameter of about 50nm and uniform distribution.
Example 4
In the embodiment, 20g of cerium carbonate and 5g of zirconium carbonate are uniformly mixed, 1.75g of ammonium chloride is uniformly dissolved in 7.5g of deionized water at 90 ℃, 0.025g of polyethylene glycol and 0.025g of cetyltrimethylammonium bromide are added, the mixture is slowly poured into 25g of mixed powder of cerium carbonate and zirconium carbonate while stirring to obtain slurry, the slurry and a certain amount of deionized water are put into a ball mill to be ball-milled for 8min at a rotating speed of about 400r/min, the ball-milled slurry is filtered by a 80-mesh filter screen and is washed and sieved by a proper amount of deionized water, and the mass fraction of the obtained emulsion/suspension is controlled to be 40%; then stirring and spray-drying the emulsion/suspension, controlling the spray-drying temperature to be 115 ℃ and the feeding amount to be 550ml/h to obtain a mixture dry powder, wherein the water content of the powder after spray-drying is not higher than 20wt%; then placing the mixture powder into a ceramic crucible, placing the ceramic crucible into a muffle furnace, and setting the heating range as follows: the temperature is 300-800 ℃ and the heating time is 30min; the temperature keeping time at 800 ℃ is 60min. Cooling to room temperature along with the furnace for 40min to obtain the nano cerium-zirconium solid solution with the particle size of 100-200 nm and uniform distribution. In this embodiment, in the calcination process, the initial temperature of calcination is 300 ℃, and rapid heating is started from 300 ℃, because rapid heating is favorable for rapid progress of the reaction and aggravates the intensity of the reaction, the particles can be rapidly formed, so as to obtain the nano cerium zirconium solid solution with larger particle size.
Example 5
In the embodiment, 20g of cerium carbonate and 5g of zirconium carbonate are uniformly mixed, 1.75g of sodium chloride is uniformly dissolved in 7.5g of deionized water at 90 ℃, 0.025g of polyethylene glycol and 0.025g of cetyltrimethylammonium bromide are added, the mixture is slowly poured into 25g of mixed powder of cerium carbonate and zirconium carbonate while stirring to obtain slurry, the slurry and a certain amount of deionized water are put into a ball mill to be ball-milled for 8min at a rotating speed of about 400r/min, the ball-milled slurry is filtered by a 80-mesh filter screen and is washed and sieved by a proper amount of deionized water, and the mass fraction of the obtained emulsion/suspension is controlled to be 40%; then stirring and spray-drying the emulsion/suspension, controlling the spray-drying temperature to be 115 ℃ and the feeding amount to be 550ml/h to obtain a mixture dry powder, wherein the water content of the powder after spray-drying is not higher than 20wt%; then placing the mixture powder into a ceramic crucible, placing the ceramic crucible into a muffle furnace, and setting the heating range as follows: the room temperature is between 800 ℃ and the time is 90 minutes; the temperature keeping time at 800 ℃ is 60min. Cooling to room temperature along with the furnace for 40min to obtain the nano cerium-zirconium solid solution with the particle size of 200-300 nm and uniform distribution. In this embodiment, the molten salt is sodium chloride, and the sodium chloride is in an ion molten state at a high temperature and interacts with the cerium-zirconium solid solution material to obtain a nano cerium-zirconium solid solution with larger particle size.
Example 6
In the embodiment, 20g of cerium carbonate and 5g of zirconium carbonate are uniformly mixed, 1.75g of sodium chloride is uniformly dissolved in 7.5g of deionized water at 90 ℃, 0.025g of polyethylene glycol and 0.025g of cetyltrimethylammonium bromide are added, the mixture is slowly poured into 25g of mixed powder of cerium carbonate and zirconium carbonate while stirring to obtain slurry, the slurry and a certain amount of deionized water are put into a ball mill to be ball-milled for 8min at a rotating speed of about 400r/min, the ball-milled slurry is filtered by a 80-mesh filter screen and is washed and sieved by a proper amount of deionized water, and the mass fraction of the obtained emulsion/suspension is controlled to be 40%; then stirring and spray-drying the emulsion/suspension, controlling the spray-drying temperature to be 115 ℃ and the feeding amount to be 550ml/h to obtain a mixture dry powder, wherein the water content of the powder after spray-drying is not higher than 20wt%; then placing the mixture powder into a ceramic crucible, placing the ceramic crucible into a muffle furnace, and setting the heating range as follows: the room temperature is between 900 ℃ and the time is 90 minutes; the temperature keeping time at 900 ℃ is 60min. Cooling to room temperature along with the furnace for 40min to obtain the nano cerium-zirconium solid solution with the particle size of 300-400 nm and uniform distribution.
By comparing example 2 with example 3, it can be obtained that the longer the holding time at the maximum temperature is, the larger the particle diameter of the nano cerium zirconium solid solution is and the smaller the variation is, under the condition that the calcining time and the maximum temperature are the same.
By comparing the examples 2 and 4, it can be obtained that the higher the initial temperature and the faster the temperature rising rate, the larger the particle diameter of the nano cerium zirconium solid solution and the larger the variation under the condition that the maximum temperature and the heat preservation time of the maximum temperature are the same.
By comparing example 2 with example 5, it can be obtained that the particle size of the nano cerium zirconium solid solution obtained by using the sodium chloride molten salt is larger than that of the ammonium chloride molten salt under the condition that the calcination time and the holding time of the maximum temperature are the same.
From comparison of example 2, example 3 and example 4, it can be found that the particle diameter of the nano cerium zirconium solid solution is at least 30nm when the maximum temperature is 800 ℃, the temperature rise time is 90min, and the heat preservation time is 60min at 800 ℃.
From comparison of example 5 and example 6, it can be derived that the higher the annealing temperature, the larger the particle size of the nano cerium zirconium solid solution, i.e., the higher the maximum temperature, the larger the particle size of the nano cerium zirconium solid solution, with the same calcination time and holding time at the maximum temperature.
The present invention is not limited to the above-mentioned embodiments, but is intended to be limited to the following embodiments, and any modifications, equivalent changes and variations in the above-mentioned embodiments can be made by those skilled in the art without departing from the scope of the present invention.
Claims (7)
1. The preparation method of the nano cerium-zirconium solid solution is characterized by comprising the following steps of:
S1, preparing mixed salt: uniformly mixing cerium salt and zirconium salt which are insoluble in water and have the mass ratio of 1:0.1-10 to obtain mixed salt; adding molten salt into water, stirring until the molten salt is dissolved, adding a dispersing agent and a surfactant, and mixing to obtain a mixed solution, wherein the molten salt is ammonium chloride or sodium chloride; gradually adding the mixed solution into the mixed salt, and mechanically stirring until the mixed solution is uniformly dispersed to obtain the required slurry; wherein the mass ratio of the mixed salt to the molten salt is 1:0.01-5, and the mass ratio of the mixed salt to the water is 1:0.1-5;
S2, adding water into the slurry, performing ball milling, and passing through a 80-mesh filter screen to obtain uniform emulsion/suspension; wherein the mass ratio of the slurry to the water is 0.5-4: 1, a step of;
s3, dripping the emulsion/suspension obtained in the step S2 into drying equipment under the stirring state for spray drying, and obtaining dry powder with the water content not higher than 20wt%;
S4, calcining the dried powder obtained in the step S3 in a furnace body, wherein the calcining stage comprises the following steps: the temperature rise rate is 0.1-50 ℃/min from room temperature to 400 ℃, the temperature rise rate is 0.1-50 ℃/min from 400-600 ℃, the temperature rise rate is 600-900 ℃, the temperature rise rate is 0.1-50 ℃/min, and the heat preservation time of the highest temperature is 30-90 min; and cooling to room temperature after calcination to obtain the nano cerium zirconium solid solution.
2. The method for preparing a nano cerium-zirconium solid solution according to claim 1, wherein the dispersant in the step S1 is polyethylene glycol.
3. The method for preparing nano cerium zirconium solid solution according to claim 1, wherein the surfactant in the step S1 is one or more of cetyl trimethyl ammonium bromide, polyethylene glycol, stearic acid and quaternary ammonium compound.
4. The method for preparing a nano cerium-zirconium solid solution according to claim 1, wherein the cerium salt in the mixed salt in step S1 is cerium carbonate or cerium oxalate, and the zirconium salt is zirconium carbonate.
5. The method for preparing nano cerium-zirconium solid solution according to claim 1, wherein in the step S2, the ball milling time is 5-10 min.
6. The method for preparing a nano cerium-zirconium solid solution according to claim 1, wherein in the step S3, the spray drying temperature is 100 to 200 ℃.
7. A nano-cerium-zirconium solid solution prepared by a method of preparing a nano-cerium-zirconium solid solution as claimed in any one of claims 1 to 6.
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| CN101058443A (en) * | 2007-05-11 | 2007-10-24 | 华东理工大学 | Method for preparing Ce-Zr based nano rare earth composite oxide |
| CN101200375A (en) * | 2007-11-16 | 2008-06-18 | 北京矿冶研究总院 | Preparation method of nano zirconium-containing series thermal barrier coating material |
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| JP4789794B2 (en) * | 2005-12-28 | 2011-10-12 | 第一稀元素化学工業株式会社 | Cerium-zirconium composite oxide and method for producing the same |
| CN109772290A (en) * | 2019-02-28 | 2019-05-21 | 江苏国盛新材料有限公司 | A kind of preparation method of cerium zirconium sosoloid |
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| CN101200375A (en) * | 2007-11-16 | 2008-06-18 | 北京矿冶研究总院 | Preparation method of nano zirconium-containing series thermal barrier coating material |
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