CN115259217B - Preparation method of metal doped nano zirconium dioxide - Google Patents
Preparation method of metal doped nano zirconium dioxide Download PDFInfo
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- CN115259217B CN115259217B CN202210881068.XA CN202210881068A CN115259217B CN 115259217 B CN115259217 B CN 115259217B CN 202210881068 A CN202210881068 A CN 202210881068A CN 115259217 B CN115259217 B CN 115259217B
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 38
- 239000002184 metal Substances 0.000 title claims abstract description 38
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 32
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007921 spray Substances 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 150000003754 zirconium Chemical class 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 15
- 230000032683 aging Effects 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 4
- 238000005507 spraying Methods 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 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 4
- 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 4
- 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 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001728 nano-filtration Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000001223 reverse osmosis Methods 0.000 claims description 4
- 238000000108 ultra-filtration Methods 0.000 claims 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 claims description 4
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 3
- 229940102253 isopropanolamine Drugs 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 150000001414 amino alcohols Chemical class 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 2
- 238000005374 membrane filtration Methods 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 2
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims description 2
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- 238000001914 filtration Methods 0.000 abstract description 5
- 238000005215 recombination Methods 0.000 abstract description 2
- 230000006798 recombination Effects 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- 238000001694 spray drying Methods 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000000746 purification Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method of metal doped nano zirconium dioxide, which comprises the steps of preparing doped metal salt into doped metal salt aqueous solution, preparing zirconium salt into zirconium salt aqueous solution, performing alkali lye hydrothermal reaction and high-temperature high-pressure hydrothermal refining reaction, then aging, solid-liquid separation, filtering and washing to obtain purified slurry, forming a spray state by adopting a spray mode to perform nano spheroidization on the purified slurry and high-pressure nano water vapor, then performing high-temperature spray drying, and performing high-temperature spray free-falling roasting on the dried powder by a high-temperature spray roasting furnace to obtain the metal doped nano zirconium dioxide. The metal doped nano zirconium dioxide prepared by the method has uniform granularity, good granular feel, small granularity, good transparency, good doping recombination, higher compatibility and higher toughness.
Description
Technical Field
The invention relates to a preparation method of metal doped nano zirconium dioxide, belonging to the technical field of nano material preparation.
Background
The nano zirconia has good thermochemical stability, high-temperature conductivity, higher strength and toughness, good mechanical, thermal, electrical and optical properties, and is widely used in various fields, in particular in the aspects of structural and functional ceramic materials. The nano zirconia is compounded with other materials, and the properties of the nano zirconia doped with different elements are utilized, so that the performance and the application of the material can be greatly improved, for example, the material can be applied to manufacturing of high-performance solid battery electrodes.
The metal doped nano zirconium dioxide prepared by the existing preparation process has poor compoundability and large brittleness, so a new preparation method of the metal doped nano zirconium dioxide is needed.
Disclosure of Invention
Aiming at the defects, the invention provides a preparation method of metal doped nano zirconium dioxide, which adopts the following technical scheme:
the preparation method of the metal doped nano zirconium dioxide is characterized in that the nano zirconium dioxide is doped with at least one or more elements of aluminum, cerium, lanthanum, gadolinium, erbium and ytterbium, and the preparation method is as follows:
and step 1, dissolving doped metal salt in water to prepare a doped metal salt aqueous solution, and dissolving zirconium salt in water to prepare a zirconium salt aqueous solution, wherein the doped metal salt and the zirconium salt are respectively 1:5-10.
And 2, adding 0.2-5% of zirconium salt active dispersing agent into the zirconium salt aqueous solution, uniformly stirring, heating to 50-90 ℃, slowly adding the metal salt-doped aqueous solution, simultaneously adding alkali liquor to adjust pH to 8-10, and carrying out distillation reflux at 80-120 ℃ for 1-20 h after the dripping is finished.
And 3, after the reaction in the step 2 is finished, adding a proper amount of active dispersing agent, slowly adding alkali liquor to adjust the PH=8.5-11, heating to 150-200 ℃, maintaining the pressure in the kettle at 0.5-1 MPa, maintaining the pressure for 1-70 h, and cooling and aging after the reaction is finished.
And 4, performing solid-liquid separation on the aged slurry, adding water into the separated material, performing ultrafiltration, nanofiltration and high-pressure reverse osmosis membrane filtration, and then washing to obtain purified slurry.
And step 5, performing nano spheroidization on the purified slurry and high-pressure nano water vapor in a spray mode, rapidly spraying and drying at high temperature, and performing high-temperature spray free-falling roasting on the dried powder by a high-temperature spray roasting furnace to obtain the metal doped nano zirconium dioxide.
Preferably, the doped metal salt is one or more of aluminum chloride, aluminum nitrate, cerium acetate, cerium chloride, cerium nitrate, lanthanum chloride, lanthanum nitrate, gadolinium nitrate, yttrium nitrate, sodium silicate, erbium chloride, ytterbium chloride and ytterbium nitrate.
Preferably, the zirconium salt is one or more of zirconium acetate, zirconium oxychloride, zirconium nitrate and zirconium sulfate.
Preferably, the active dispersing agent is one or more of ethanolamine, isopropanolamine, polyethylene glycol, soaps, acids, fatty acids, polyalcohols and amino alcohols.
Preferably, the aging temperature in the step 3 is 80-120 ℃ and the aging time is 1-90 h.
Preferably, the calcination temperature in step 5 is 450-1000 ℃.
Compared with the prior art, the invention has the beneficial effects that: the metal doped nano zirconium dioxide prepared by the method has uniform granularity, good granular feel, small granularity, good transparency, good doping recombination, higher compatibility and higher toughness.
Drawings
FIG. 1 is a SEM image of a metal-doped nano zirconium dioxide of the present invention;
FIG. 2 is an XRD pattern for metal doped nano zirconium dioxide of the present invention.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings and examples.
Example 1:
aluminum chloride, cerium acetate and deionized water are stirred and mixed uniformly according to the mass ratio of 1:1:10 to prepare a doped metal salt aqueous solution, zirconium acetate and deionized water are added into a reaction kettle according to the mass ratio of 2:7 to prepare a zirconium salt aqueous solution. Adding polyethylene glycol and amine active dispersing agent into zirconium salt aqueous solution, stirring uniformly, heating to 65 ℃, slowly adding doped metal salt aqueous solution at a speed of 1.5kg/min, simultaneously adding ammonia water to adjust pH to 8.5, distilling and refluxing at 85 ℃ for 10 hours after the dripping is finished, and keeping a stirring state in the whole reaction. After the reaction, oleic acid is added, ammonia water is slowly added at the speed of 0.2kg/min to adjust the PH=9.5, the temperature is increased to 180 ℃ at the speed of 1.5 ℃/min, the pressure in the kettle is maintained at 0.8MPa, the reaction is maintained for 35 hours, and the whole reaction is kept in a stirring state. Cooling to 80 ℃ after the reaction is finished, aging for 50 hours, cooling to 30 ℃ after aging, performing solid-liquid separation, adding deionized water into the separated materials, filtering by adopting one or more modes of ultrafiltration, nanofiltration and high-pressure reverse osmosis membranes, and washing with water after filtering to obtain purified slurry. And (3) adopting a spray mode to form a spray state with the purified slurry and high-pressure nanometer water vapor to carry out nanometer spheroidization, then rapidly spraying and drying at high temperature, and carrying out high-temperature spray free-falling roasting at 950 ℃ on the dried powder by a high-temperature spray roasting furnace to obtain the metal doped nanometer zirconium dioxide.
Example 2:
gadolinium nitrate, cerium acetate and deionized water are stirred and mixed uniformly according to the mass ratio of 1:2:11 to prepare a doped metal salt aqueous solution, zirconium acetate and deionized water are added into a reaction kettle according to the mass ratio of 3:8 to prepare a zirconium salt aqueous solution. Adding an ethanolamine active dispersing agent into a zirconium salt aqueous solution, uniformly stirring, heating to 70 ℃, slowly adding a doped metal salt aqueous solution at a speed of 2kg/min, simultaneously adding ammonia water to adjust PH=8, distilling and refluxing at a temperature of 90 ℃ for 5 hours after the dripping is finished, and keeping a stirring state in the whole reaction. After the reaction is finished, isopropanolamine is added, ammonia water is slowly added at the speed of 0.8kg/min to adjust PH=9, then the temperature is increased to 200 ℃ at the speed of 2 ℃/min, the pressure in the kettle is maintained at 0.9MPa, the reaction is maintained for 45h, and the whole reaction is kept in a stirring state. Cooling to 90 ℃ after the reaction is finished, aging for 40 hours, cooling to 25 ℃ after aging, performing solid-liquid separation, adding deionized water into the separated materials, filtering by adopting one or more modes of ultrafiltration, nanofiltration and high-pressure reverse osmosis membranes, and washing with water after filtering to obtain purified slurry. And (3) adopting a spray mode to form a spray state with the purified slurry and high-pressure nanometer water vapor to carry out nanometer spheroidization, then rapidly spraying and drying at high temperature, and carrying out high-temperature spray free-falling roasting at 1000 ℃ on the dried powder by a high-temperature spray roasting furnace to obtain the metal doped nanometer zirconium dioxide.
In the invention, the opposite spraying of the purification slurry and the high-pressure nano water vapor can be realized by two spraying devices which are arranged oppositely, one spraying purification slurry and the other spraying high-pressure nano water vapor, and the sprayed high-speed purification slurry flow and the nano water vapor flow are strongly opposite. The high-temperature injection free-falling roasting can be realized through an injection device and a vertical roasting furnace, the injection device can be one or two injection devices which are horizontally arranged in opposite directions, the dried powder is injected into the roasting furnace through the injection device, and the powder is roasted and discharged in the furnace in a free-falling mode. The spraying device may be a sprayer or an injector or a spray nozzle.
Fig. 1 is an SEM image of the metal doped nano zirconium dioxide of the present invention, and it can be seen from the image that the metal doped nano zirconium dioxide prepared by the present invention has small particles, uniform and uniform size, strong particle feel, size of about 15nm, and clear and smooth contour.
Fig. 2 is an XRD pattern of the metal doped nano zirconium dioxide, and the metal doped nano zirconium dioxide prepared by the invention has complete crystal form and good crystallinity.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, such changes and modifications are also intended to be within the scope of the invention.
Claims (3)
1. The preparation method of the metal doped nano zirconium dioxide is characterized in that the metal doped nano zirconium dioxide is doped with at least one or more elements of aluminum, cerium, lanthanum, gadolinium, erbium and ytterbium, and the preparation method is as follows:
step 1, dissolving doped metal salt in water to prepare a doped metal salt aqueous solution, and dissolving zirconium salt in water to prepare a zirconium salt aqueous solution, wherein the doped metal salt and the zirconium salt are respectively 1:5-10;
step 2, adding 0.2-5% of zirconium salt active dispersant into the zirconium salt aqueous solution, uniformly stirring, heating to 50-90 ℃, slowly adding the metal salt aqueous solution, simultaneously adding alkali liquor to adjust pH=8-10, and carrying out distillation reflux at 80-120 ℃ for 1-20 h after the dripping is finished;
step 3, after the reaction of the step 2 is finished, adding a proper amount of active dispersing agent, slowly adding alkali liquor to adjust the PH=8.5-11, heating to 150-200 ℃, maintaining the pressure in the kettle at 0.5-1 MPa, maintaining the pressure for 1-70 h, cooling to 80-120 ℃ after the reaction is finished, and aging for 1-90 h;
step 4, performing solid-liquid separation on the aged slurry, adding water into the separated material, performing ultrafiltration, nanofiltration and high-pressure reverse osmosis membrane filtration, and then washing to obtain purified slurry;
step 5, performing nano spheroidization on the purified slurry and high-pressure nano water vapor in a spray mode, then rapidly spraying and drying at high temperature, and performing high-temperature spray free-falling roasting on the dried powder by a high-temperature spray roasting furnace to obtain metal doped nano zirconium dioxide;
the doped metal salt is one or more of aluminum chloride, aluminum nitrate, cerium acetate, cerium chloride, cerium nitrate, lanthanum chloride, lanthanum nitrate, gadolinium nitrate, yttrium nitrate, sodium silicate, erbium chloride, ytterbium chloride and ytterbium nitrate;
the zirconium salt is one or more of zirconium acetate, zirconium oxychloride, zirconium nitrate and zirconium sulfate.
2. The method for preparing metal-doped nano zirconium dioxide according to claim 1, wherein the active dispersing agent is one or more of ethanolamine, isopropanolamine, polyethylene glycol, soaps, acids, fatty acids, polyalcohols and amino alcohols.
3. The method for preparing metal-doped nano zirconium dioxide according to claim 1, wherein the roasting temperature in step 5 is 450-1000 ℃.
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| CN115259217B true CN115259217B (en) | 2023-12-01 |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1524795A (en) * | 2003-02-28 | 2004-09-01 | 中国石油化工股份有限公司 | Preparing process of zirconia |
| CN101698509A (en) * | 2009-09-11 | 2010-04-28 | 淄博广通化工有限责任公司 | Method for producing nano zirconia |
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| CN1524795A (en) * | 2003-02-28 | 2004-09-01 | 中国石油化工股份有限公司 | Preparing process of zirconia |
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