CN114433061A - 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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- CN114433061A CN114433061A CN202011231675.9A CN202011231675A CN114433061A CN 114433061 A CN114433061 A CN 114433061A CN 202011231675 A CN202011231675 A CN 202011231675A CN 114433061 A CN114433061 A CN 114433061A
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- 239000006104 solid solution Substances 0.000 title claims abstract description 64
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 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 39
- 239000002002 slurry Substances 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 25
- 238000001354 calcination Methods 0.000 claims abstract description 23
- 238000001694 spray drying Methods 0.000 claims abstract description 23
- 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 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 150000003754 zirconium Chemical class 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000012216 screening Methods 0.000 claims abstract description 4
- 235000002639 sodium chloride Nutrition 0.000 claims description 49
- 150000003839 salts Chemical class 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 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 compound [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
- 238000002156 mixing Methods 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 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
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 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
- DAWBXZHBYOYVLB-UHFFFAOYSA-J oxalate;zirconium(4+) Chemical compound [Zr+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O DAWBXZHBYOYVLB-UHFFFAOYSA-J 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000001508 potassium citrate Substances 0.000 claims description 2
- 229960002635 potassium citrate Drugs 0.000 claims description 2
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 2
- 235000011082 potassium citrates Nutrition 0.000 claims description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 30
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 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
- 230000002776 aggregation Effects 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229910000420 cerium oxide Inorganic materials 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 238000005054 agglomeration Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000011812 mixed powder Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000009827 uniform distribution Methods 0.000 description 5
- 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 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- -1 rare earth carbonate Chemical class 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 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
- 230000008859 change Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 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
- 239000012716 precipitator Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 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 2
- 150000000914 Dysprosium Chemical class 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 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
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005406 washing 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
-
- B01J35/40—
-
- B01J35/60—
-
- 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
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 screening by a filter screen of 80 meshes to obtain uniform emulsion/suspension; s3, dripping the emulsion/suspension obtained in the step S2 into a drying device under the stirring state for spray drying, and obtaining dry powder with the water content not higher than 20 wt%; and S4, calcining the dried powder obtained in the step S3 in a furnace body, and cooling to room temperature after calcination 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 particle size and uniform particle size distribution. The invention also provides a nano cerium zirconium solid solution.
Description
Technical Field
The invention relates to the field of material preparation, and particularly provides a preparation method of a nano cerium-zirconium solid solution. The invention also provides a nano cerium zirconium solid solution.
Technical Field
With the rapid development of the automobile industry, the pollution of automobile exhaust has attracted general attention of society, and the catalytic purification of automobile exhaust by adopting a three-way catalyst (TWC) is one of the main approaches for solving the problem of the pollution of the exhaust at present. Since the beginning of the 80 s of the last century, cerium oxide-based high-performance rare earth oxygen storage materials have been widely applied to automobile exhaust purification three-way catalysts, become key materials of the three-way catalysts, determine the performance and the service life of the catalysts, and are the focus of competition of various enterprises in the field of automobile exhaust purification catalysts. Since pure cerium oxide has poor aging resistance, it substantially loses oxygen storage capacity when the firing temperature is higher than 850 ℃. Research results show that the cerium oxide can be added with a proper amount of zirconium to remarkably improve the thermal stability and the oxygen storage performance of the cerium oxide, so that the cerium-zirconium solid solution becomes a second-generation oxygen storage material of the automobile exhaust purification catalyst. Although the oxygen storage performance and the anti-aging performance of the cerium-zirconium solid solution are obviously superior to those of pure cerium oxide, and a high oxygen storage amount can be maintained even when the cerium-zirconium solid solution is obviously sintered at a high temperature, the performance of the three-way catalyst for purifying automobile exhaust, particularly the thermal stability and the oxygen storage performance of an oxygen storage material, still needs to be further improved along with the continuous increase of the automobile holding amount and the increasing severity of environmental pollution.
At present, the preparation method of the cerium-zirconium solid solution mainly comprises a coprecipitation method, a sol-gel method, a microemulsion method, a hydrothermal method, a high-energy ball milling method and the like. The coprecipitation method is widely applied due to the advantages of simple process, easy control of conditions, good product uniformity, low production cost, convenience for industrial production and the like, but the existing coprecipitation method has various processes, and the performance of the prepared cerium-zirconium solid solution can not meet the requirements of the automobile exhaust purification catalyst in certain aspects, such as oxygen storage capacity, thermal stability or specific surface area.
At present, the main method for preparing the cerium-zirconium solid solution is a soluble salt precipitation method, for example, patent application No. CN201910149653.9 discloses a preparation method of a nano cerium-zirconium solid solution, and specifically discloses a method for preparing the cerium-zirconium solid solution by adding ethylene 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 adjust the pH to 8-9, precipitating for 8 hours, and finally centrifuging, washing, drying and calcining to prepare the cerium-zirconium solid solution with large specific surface area, good oxygen storage performance and good thermal stability. The acid radical ions brought by a large amount of soluble salts in the invention can generate great environmental protection problems, and the investment in environmental protection is increased, so that the production cost is increased, and the grain diameter of the grains grows very obviously when the nano oxide is calcined, and becomes a 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 particularly discloses a method for preparing the nano cerium-zirconium solid solution, which comprises the steps of firstly dissolving cerium carbonate, zirconium carbonate and doped rare earth carbonate in concentrated nitric acid respectively to obtain a cerium nitrate solution, a zirconium nitrate solution and a doped rare earth nitrate solution, blending to obtain a mixed salt solution, and then adding hydrogen peroxide; adding a surfactant after the precipitant is prepared into a solution, and dividing into at least two parts; dripping the mixed salt solution into a precipitator solution by a pH swing precipitation method; finally, the precipitate is aged, washed, roasted and screened by a pair of rollers to obtain the cerium-zirconium solid solution. Said invention also can greatly raise cost, at the same time can make a certain influence on product purity, and when the nano oxide is calcined, the grain size of the grain can be obviously grown, and can be formed into submicron grade oxide.
In the prior art of the precipitation method, the concentration of a reaction system is not uniform due to titration of a precipitator in a dysprosium salt solution, the growth speed of dysprosium 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 complicated equipment, various variables need to be controlled, the particle size distribution range of the powder is not adjustable, and the nano cerium-zirconium solid solution prepared by a hydrothermal method has serious agglomeration phenomenon and difficult separation.
Disclosure of Invention
In order to solve the problems of product purity 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 preparation method. Is easy for industrialized production.
A preparation method of a nano cerium zirconium solid solution comprises the following steps:
s1, preparing slurry: uniformly mixing water-insoluble cerium salt and zirconium salt in a 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 water is 1: 0.1-5;
s2, adding water into the slurry, performing ball milling, and screening by a filter screen of 80 meshes to obtain uniform emulsion/suspension; wherein the mass ratio of the slurry to the water is 0.5-4: 1;
s3, dripping the emulsion/suspension obtained in the step S2 into a drying device under the stirring state for spray drying, and obtaining dry powder with the water content not higher than 20 wt%;
s4, calcining the dried powder obtained in the step S3 in a furnace body, wherein the calcining stage comprises the following steps: the temperature is raised from room temperature to 400 ℃ at a rate of 0.1-50 ℃/min, 400-600 ℃ at a rate of 0.1-50 ℃/min, 600-900 ℃ at a rate of 0.1-50 ℃/min, and the holding time at the highest temperature is 0-300 min; and cooling to room temperature after calcining to obtain the nano cerium-zirconium solid solution.
Further, the dispersant in 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, cerium acetate or cerium oxalate, and the zirconium salt is zirconium carbonate, zirconium acetate or zirconium oxalate.
Further, in step S1, the molten salt is one or more of ammonium chloride, sodium chloride, potassium chloride, sodium fluoride, ammonium carbonate, ammonia water, sodium carbonate, potassium carbonate, ammonium citrate, sodium citrate, or potassium citrate.
Further, in step S2, the ball milling time is 5 to 10 min.
Further, in step S3, the temperature of spray drying 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.
Has the advantages 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 size of 30 nanometers, uniform particle size, good dispersibility, high calcination temperature and complete crystal growth.
2. The preparation method of the nano cerium-zirconium solid solution is simple and stable, has few processes, low requirements on equipment, few types of used raw materials, no toxicity, no pollution and low production cost, and can generate tail gas which is easy to absorb and treat; in addition, the added polyethylene glycol and a certain amount of surfactant enable the produced nano cerium-zirconium solid solution to be spherical-like, high in purity, free of agglomeration, narrow in particle size distribution and easy to disperse.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of protection 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 water-insoluble cerium salt and zirconium salt in a 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 water is 1: 0.1-5;
s2, adding water into the slurry, performing ball milling, and screening by a filter screen of 80 meshes to obtain uniform emulsion/suspension; wherein the mass ratio of the slurry to the water is 0.5-4: 1;
s3, dripping the emulsion/suspension obtained in the step S2 into a drying device under the stirring state for spray drying, and obtaining dry powder with the water content not higher than 20 wt%;
s4, calcining the dried powder obtained in the S3 in a furnace, wherein the calcining stage comprises the following steps: the temperature is raised from room temperature to 400 ℃ at a rate of 0.1-50 ℃/min, 400-600 ℃ at a rate of 0.1-50 ℃/min, 600-900 ℃ at a rate of 0.1-50 ℃/min, and the holding time at the highest temperature is 0-300 min; and cooling to room temperature after calcining to obtain the nano cerium-zirconium solid solution.
In this embodiment, the mass of the dispersant and the surfactant is one thousandth to ten thousandth of the mass of the solid raw material, respectively, and in a preferred embodiment, the mass of the dispersant and the surfactant is three thousandth of the fixed mass of the raw material, respectively.
In this embodiment, the mechanical stirring and dispersing manner used in step S1 is mechanical stirring at room temperature, and the mechanical stirring and dispersing function is to uniformly mix the two water-insoluble cerium salts and zirconium salts, and to sufficiently mix and disperse the molten salt 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;
in the step S2, the ball milling time is 5-10 min; the ball milling has the following functions: the two water-insoluble cerium salts and the two water-insoluble zirconium salts 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 two water-insoluble zirconium salts; because the cerium salt and the zirconium salt which are not dissolved in water are dissociated under the action of mechanical force, free electrovalence bonds can be generated on a new section, and particle molecules are aggregated mutually, so that the aggregation of the calcined particles is more serious, the accelerated combination of the cerium salt particle molecules and the zirconium salt particle molecules is accelerated, positive ions and negative ions generated by dissociation of a molten salt solution in an aqueous solution can be adsorbed on the surface of a ball-milled product, and the aggregation phenomenon of the particles can be effectively inhibited;
the spray drying temperature in the step S3 is 100-200 ℃, and the spray drying is adopted to aim at refining and homogenizing the precursor, so that the molten salt can be adsorbed on the surfaces of two water-insoluble cerium salts and zirconium salts more uniformly and effectively;
in step S4, the crystallization of the nano-cerium-zirconium solid solution is promoted by the calcination temperature, the time for raising the temperature to the maximum temperature and the maximum temperature holding time, and the size of the crystal grains of the nano-cerium-zirconium solid solution can be controlled, wherein the holding time for the maximum temperature is 30-90 min, and the calcination process specifically includes: from room temperature to 400 ℃, the heating rate is 0.1-50 ℃/min, the heating time is 0-90 min, the preheating process activates the raw materials, particularly molten salt, and part of the molten salt begins to dissolve or decompose; the temperature rise rate is 0.1-50 ℃/min at 400-600 ℃, the temperature rise time is 0-90 min, the molten salt accelerates the decomposition kinetic rate of two cerium salts and zirconium salts which are insoluble in water, promotes the crystallization of oxides and the doping of zirconium elements in cerium oxide lattices to form cerium-zirconium solid solutions, the molten salt is decomposed at high temperature, the generated ascending hot air flow can break partial agglomeration or a precursor or the cerium-zirconium solid solutions with the agglomeration tendency to a certain extent, the growth and agglomeration of cerium-zirconium solid solution crystal nuclei are effectively prevented, and the dispersion function of particles of the cerium-zirconium solid solutions is retained by the molten salt through a grinding aid mechanism; 600-900 ℃, the heating rate is 0.1-50 ℃/min, the heating time is 0-90 min, the time period aims at the rapid forming of the cerium-zirconium solid solution crystal nucleus and the growth of crystal grains, the crystal nucleus of the cerium-zirconium solid solution product is rapidly formed at high temperature, the growth and agglomeration of the crystal nucleus of the cerium-zirconium solid solution are effectively prevented by the existence of molten salt, and the particle size of the particles is controlled to a certain extent; finally, the temperature is reduced with the furnace body or is quickly reduced after the temperature is reduced, and the nano cerium-zirconium solid solution is prepared; the furnace body used for calcining is a muffle furnace, a tubular furnace, a rotary furnace, a crucible resistance furnace, a box-type furnace, a lifting furnace, a pit furnace, a trolley furnace, a mesh belt furnace, a roller kiln, a push plate kiln, a tunnel furnace, a rotary kiln, a suspension calciner or the calcining 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 this 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 hexadecyl trimethyl ammonium bromide are added, then the mixture is slowly poured into 25g of mixed powder of cerium carbonate and zirconium carbonate while being stirred 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 sieved by an 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 the emulsion/suspension liquid and spray-drying at the same time, controlling the spray-drying temperature to be 115 ℃ and the feeding amount to be 550ml/h to obtain mixture dry powder, wherein the water content of the powder after spray-drying is not higher than 20 wt%; then placing the mixture powder into a ceramic crucible, placing the ceramic crucible into a muffle furnace, and setting the temperature rise range as follows: the room temperature is 800 ℃, and the temperature rise time is 90 min; the temperature is kept at 800 ℃ for 60 min. Cooling to room temperature along with the furnace, and cooling for 40min to obtain the nano cerium zirconium solid solution with the particle size of about 30nm and uniform distribution.
Example 3
In this 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 hexadecyl trimethyl ammonium bromide are added, then the mixture is slowly poured into 25g of mixed powder of cerium carbonate and zirconium carbonate while being stirred 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 sieved by an 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 the emulsion/suspension liquid and spray-drying at the same time, controlling the spray-drying temperature to be 115 ℃ and the feeding amount to be 550ml/h to obtain mixture dry powder, wherein the water content of the powder after spray-drying is not higher than 20 wt%; then placing the mixture powder into a ceramic crucible, placing the ceramic crucible into a muffle furnace, and setting the temperature rise range as follows: the room temperature is 800 ℃, and the temperature rise time is 60 min; the temperature of 800 ℃ is kept for 90 min. Cooling to room temperature along with the furnace, and cooling for 40min to obtain the nano cerium zirconium solid solution with the particle size of about 50nm and uniform distribution.
Example 4
In this 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 hexadecyl trimethyl ammonium bromide are added, then the mixture is slowly poured into 25g of mixed powder of cerium carbonate and zirconium carbonate while being stirred 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 sieved by an 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, and obtaining mixture dry powder, wherein the water content of the powder after spray-drying is not higher than 20 wt%; then placing the mixture powder into a ceramic crucible, placing the ceramic crucible into a muffle furnace, and setting the temperature rise range as follows: heating for 30min at 300-800 ℃; the temperature is kept at 800 ℃ for 60 min. 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, during the calcination process, the initial temperature of the calcination is 300 ℃, and the rapid heating is started from 300 ℃, because the rapid heating is beneficial to the rapid progress of the reaction, and the severity of the reaction is increased, so that the particles can be rapidly molded to obtain the nano cerium-zirconium solid solution with larger particle size.
Example 5
In this 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, then the mixture is slowly poured into 25g of mixed powder of cerium carbonate and zirconium carbonate while being stirred 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 sieved by an 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 the emulsion/suspension liquid and spray-drying at the same time, controlling the spray-drying temperature to be 115 ℃ and the feeding amount to be 550ml/h to obtain mixture dry powder, wherein the water content of the powder after spray-drying is not higher than 20 wt%; then placing the mixture powder into a ceramic crucible, placing the ceramic crucible into a muffle furnace, and setting the temperature rise range as follows: the temperature is between room temperature and 800 ℃, and the time is 90 min; the temperature is kept at 800 ℃ for 60 min. 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, which 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 a large particle size.
Example 6
In this 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, then the mixture is slowly poured into 25g of mixed powder of cerium carbonate and zirconium carbonate while being stirred 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 sieved by an 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 the emulsion/suspension liquid and spray-drying at the same time, controlling the spray-drying temperature to be 115 ℃ and the feeding amount to be 550ml/h to obtain mixture dry powder, wherein the water content of the powder after spray-drying is not higher than 20 wt%; then placing the mixture powder into a ceramic crucible, placing the ceramic crucible into a muffle furnace, and setting the temperature rise range as follows: the temperature is between room temperature and 900 ℃, and the time is 90 min; the temperature of 900 ℃ is kept for 60 min. 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 seen that the longer the soaking time at the maximum temperature is, the larger the particle size of the nano cerium zirconium solid solution is, and the smaller the change is, in the case where the calcination time and the maximum temperature are the same.
By comparing example 2 with example 4, it can be seen that the particle size of the nano cerium zirconium solid solution is larger and the change is larger when the initial temperature is higher and the temperature rising rate is faster under the condition that the maximum temperature and the holding time at the maximum temperature are the same.
By comparing example 2 with example 5, it can be seen 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 at the maximum temperature are the same.
By comparing example 2, example 3 and example 4, it can be shown that when the maximum temperature is 800 ℃, the temperature rise time is 90min, and the holding time at 800 ℃ is 60min, the particle size of the nano cerium zirconium solid solution is 30nm at the minimum.
By comparing example 5 with example 6, it can be seen that the higher the annealing temperature is, the larger the particle size of the nano ceria-zirconia solid solution is, that is, the higher the maximum temperature is, the larger the particle size of the nano ceria-zirconia solid solution is, in the case where the calcination time and the holding time at the maximum temperature are the same.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
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 water-insoluble cerium salt and zirconium salt in a 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 water is 1: 0.1-5;
s2, adding water into the slurry, performing ball milling, and screening by a filter screen of 80 meshes to obtain uniform emulsion/suspension; wherein the mass ratio of the slurry to the water is 0.5-4: 1;
s3, dripping the emulsion/suspension obtained in the step S2 into a drying device under the stirring state for spray drying, and obtaining dry powder with the water content not higher than 20 wt%;
s4, calcining the dried powder obtained in the step S3 in a furnace body, wherein the calcining stage comprises the following steps: the temperature is raised from room temperature to 400 ℃ at a rate of 0.1-50 ℃/min, 400-600 ℃ at a rate of 0.1-50 ℃/min, 600-900 ℃ at a rate of 0.1-50 ℃/min, and the holding time at the highest temperature is 0-300 min; and cooling to room temperature after calcining to obtain the nano cerium-zirconium solid solution.
2. The method of claim 1, wherein the dispersant in step S1 is polyethylene glycol.
3. The method of claim 1, wherein the surfactant in step S1 is one or more selected from cetyl trimethyl ammonium bromide, polyethylene glycol, stearic acid and quaternary ammonium compound.
4. The method of claim 1, wherein the cerium salt in the mixed salt in step S1 is cerium carbonate, cerium acetate or cerium oxalate, and the zirconium salt is zirconium carbonate, zirconium acetate or zirconium oxalate.
5. The method of claim 1, wherein the molten salt in step S1 is one or more selected from ammonium chloride, sodium chloride, potassium chloride, sodium fluoride, ammonium carbonate, ammonia water, sodium carbonate, potassium carbonate, ammonium citrate, sodium citrate, and potassium citrate.
6. The method for preparing a nano cerium zirconium solid solution according to claim 1, wherein in step S2, the ball milling time is 5-10 min.
7. The method of claim 1, wherein the spray drying temperature in step S3 is 100-200 ℃.
8. A nano ceria-zirconia solid solution, characterized in that it is prepared by the method of any one of claims 1 to 7.
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