CN103771513B - A kind of high dispersion nanometer oxide zirconium raw powder's production technology - Google Patents
A kind of high dispersion nanometer oxide zirconium raw powder's production technology Download PDFInfo
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Abstract
The invention discloses a kind of high dispersion nanometer oxide zirconium raw powder's production technology, in the aqueous solution containing zirconates, add alkaline precipitating agent obtain colloidal precipitation of hydroxide, again successively through filtering, washing and dehydration acquisition dry hydrogen oxide precipitation, finally pulverize and obtain Zirconium powder, the drying mode that subcritical fluids is dewatered is adopted in the process of described dehydration, described subcritical fluids is dry is medium with liquefied ammonia, at 50 ~ 80 DEG C of temperature and pH value under 8.8 ~ 9.2 states, by the moisture removal in precipitation of hydroxide.Preparation method of the present invention, effectively can avoid the reunion of powder in nano zircite preparation process, obtain the nano zircite product of high purity, high degree of dispersion, high-ratio surface, and have that Production Flow Chart is simple, cost and energy consumption is low, the advantage that is easy to suitability for industrialized production.
Description
Technical field
The invention belongs to field of fine chemical, be specifically related to a kind of preparation method of nano zirconium oxide powder.
Background technology
Zirconium white is white heavy amorphous powder or monoclinic crystal, and odorless is tasteless.Zirconium dioxide has three kinds of crystal formations, and low temperature is oblique system, density 5.65g/cm
3; Tetragonal system is formed, density 6.10g/cm more than 1100 DEG C
3; More than 2370 DEG C, form isometric system, density is 6.27g/cm
3.Zirconium dioxide is the metal oxide uniquely with acidity, alkalescence, oxidisability and reductibility, and its chemical stability is very high, is only soluble in hydrofluoric acid in various acid.Zirconium dioxide has fusing point and boiling point is high, hardness is large, be isolator under normal temperature, then there is the advantageous properties such as electroconductibility under high temperature.Zirconia material has high rigidity, high strength, high tenacity, the physical and chemical performance that high wear resistance and chemical resistance etc. are excellent, zirconium white has obtained at catalyzer and the various field of support of the catalyst, pottery, refractory materials, machinery, electronics, optics, opticfiber communication, clock and watch ornaments, aerospace, biology, chemistry etc. and has applied widely.
In order to better meet various requirement, prepare High Purity, evenly and the powder of the little nano zircite of reunion degree seems particularly important.Nano zircite preparation method mainly contains chemical precipitation method, hydrolysis method, hydrothermal method, alcohol one aqueous solution heating method, sol-gel method etc.The major drawbacks of these methods is, from the washing being formed into precipitation of colloidal precipitation, drying and calcining, each stage all may produce the reunion of particle.Such aggregation procedure is irreversible, and agglomeration will cause grain growth, causes specific surface area sharply to decline, and has a strong impact on the processing performance of powder.Therefore, how effectively the moisture removed in co-precipitation is the important means reducing and eliminate coacervate in powder.Patent CN1168785C adopts azeotropic distn to dewater when preparing nano zirconium oxide powder, dewater to hydronium(ion) zirconium white gel for entrainment agent with butanols, ethanol etc., it can reduce the formation of powder hard aggregation, but the temperature requirement of dehydration is higher; The people such as Liang Li duckweed, Dang Shue adopt gel-supercritical fluid drying technique to synthesize the stabilization ZrO of Different Ca O concentration
2ultrafine powder, but the method power consumption is large, and easily cause the reunion (silicate is circulated a notice of, 2002:83 ~ 85) of Zirconium powder.
Summary of the invention
The object of this invention is to provide a kind of preparation method of nano zircite, overcome the deficiency existed in current study of preparation of nano-zirconia using chemical precipitation method liquid phase method technique, to obtain the nano zirconium oxide powder of high purity, high degree of dispersion, high-ratio surface.
The concrete technical scheme of the present invention is as follows: a kind of high dispersion nanometer oxide zirconium raw powder's production technology, in the aqueous solution containing zirconates, add alkaline precipitating agent obtain colloidal precipitation of hydroxide, again successively through filtering, washing and dehydration obtain dry hydrogen oxide precipitation, finally pulverize and obtain Zirconium powder, the drying mode that subcritical fluids is dewatered is adopted in the process of described dehydration, described subcritical fluids is dry is medium with liquefied ammonia, at 50 ~ 80 DEG C of temperature, vacuumize pressure and pH value under 8.8 ~ 9.2 states, by the moisture removal in precipitation of hydroxide.
Further describe as to above-mentioned high dispersion nanometer oxide zirconium raw powder's production technology, the pressure of described subcritical fluids drying process medium liquefied ammonia is corresponding vapour pressure, solvent load is 1 ~ 2 times of handled quality of material, treatment time is 30 ~ 100min, and number of processes is 2 ~ 3 times; After processing containing solvent precipitation of hydroxide through decompression gasification, vacuum desolvation, namely obtain dry precipitation of hydroxide.
As to a kind of preferred version of above-mentioned high dispersion nanometer oxide zirconium raw powder's production technology, before adding alkaline precipitating agent, first add crystal phase stablizer in the aqueous solution containing zirconates.
Further describe as to above-mentioned high dispersion nanometer oxide zirconium raw powder's production technology, dried precipitation of hydroxide calcining temperature is 400 ~ 600 DEG C, calcination time is 120 ~ 240min, is conducive to like this removing the organism in powder completely, improves product purity.
The present invention compared with prior art, there is following beneficial effect and advantage: the reunion effectively can avoiding powder in study of preparation of nano-zirconia using chemical precipitation method process, obtain the nano zircite product of high purity, high degree of dispersion, high-ratio surface, and Production Flow Chart is simple, cost and energy consumption is low, the advantage that is easy to suitability for industrialized production to adopt the drying mode of subcritical fluids dehydration to have.
Embodiment
For introducing enforcement of the present invention in detail, be listed below embodiment, but protection scope of the present invention is not by the restriction of the following example, in the described embodiment, unless otherwise indicated, all per-cent all by weight.
The mensuration of powder index: X-ray diffraction analysis measures crystalline structure and the median size of powder, the granularity substep of TEM (transmission electron microscope) analysis powder and crystal morphology, BET method measures the specific surface area of powder.
Add the ammoniacal liquor (pH=10) of 200mL in the reactor, be the basic zirconium chloride (ZrOCl of 0.5mol/L by 200mL concentration under constantly stirring
28H
2o) solution controls suitable speed instillation, and regulates the pH value of reaction system to make it remain between 9.0 ± 0.2 with ammoniacal liquor, and after reaction 10h terminates, ageing, suction filtration, be washed with water in precipitation not containing Cl
-(use AgNO
3solution is checked), then use absolute ethanol washing 2 ~ 3 times, obtain colloidal precipitation of hydroxide.Then carry out dehydrating step, in the process of described dehydration, adopting the drying mode of subcritical fluids dehydration, is below the embodiment of each dehydration:
Embodiment 1
Colloidal precipitation of hydroxide is carried out dewatering and puts into the moisture eliminator of construction of pressure vessel, vacuumize and make moisture eliminator internal pressure be down to-0.08Mpa, squeeze into the liquefied ammonia solvent with raw material identical weight, carry out adverse current processed, temperature 50 C (working pressure is corresponding vapour pressure), through each process 100 minutes, after totally 2 process, emptying solvent, solvent-laden precipitation of hydroxide is through decompression gasification, gauge pressure vacuumizes precipitation after reaching 0MPa, when gauge pressure is-0.09MPa, temperature is 40 ~ 50 DEG C, maintain 60min and namely obtain dry hydrogen oxide precipitation, after pulverizing again in High Temperature Furnaces Heating Apparatus 600 DEG C calcining 120min, obtain nano zircite (ZrO
2) powder 1,
Embodiment 2
Colloidal precipitation of hydroxide is put into the moisture eliminator of construction of pressure vessel, vacuumize and make moisture eliminator internal pressure be down to-0.08Mpa, squeeze into the liquefied ammonia solvent with raw material identical weight, carry out adverse current processed, temperature 70 C (working pressure is corresponding vapour pressure), through each process 60 minutes, after totally 3 process, emptying solvent, solvent-laden precipitation of hydroxide is through decompression gasification, gauge pressure vacuumizes precipitation after reaching 0MPa, when gauge pressure is-0.09MPa, temperature is 50 ~ 60 DEG C, maintain 40min and namely obtain dry hydrogen oxide precipitation, after pulverizing again in High Temperature Furnaces Heating Apparatus 500 DEG C calcining 180min, obtain nano zircite (ZrO
2) powder 2,
Embodiment 3
Colloidal precipitation of hydroxide is put into the moisture eliminator of construction of pressure vessel, vacuumize and make moisture eliminator internal pressure be down to-0.08Mpa, squeeze into 2 times to the liquefied ammonia solvent of raw material weight, carry out adverse current processed, temperature 80 DEG C (working pressure is corresponding vapour pressure), through each process 30 minutes, after totally 3 process, emptying solvent, solvent-laden precipitation of hydroxide is through decompression gasification, gauge pressure vacuumizes precipitation after reaching 0MPa, when gauge pressure is-0.09MPa, temperature is 50 ~ 60 DEG C, maintain 60min and namely obtain dry hydrogen oxide precipitation, after pulverizing again in High Temperature Furnaces Heating Apparatus 400 DEG C calcining 240min, obtain nanometer ZrO
2powder 3,
Embodiment 4
The colloidal precipitation of hydroxide of preparation is put into the moisture eliminator of construction of pressure vessel, vacuumize and make moisture eliminator internal pressure be down to-0.08Mpa, squeeze into the liquefied ammonia solvent with raw material identical weight, carry out adverse current processed, temperature 40 DEG C (working pressure is corresponding vapour pressure), through each process 60 minutes, after totally 3 process, emptying solvent, solvent-laden precipitation of hydroxide is through decompression gasification, gauge pressure vacuumizes precipitation after reaching 0MPa, when gauge pressure is-0.09MPa, temperature is 50 ~ 60 DEG C, maintain 60min and namely obtain dry hydrogen oxide precipitation, after pulverizing again in High Temperature Furnaces Heating Apparatus 400 DEG C calcining 240min, obtain nanometer ZrO
2powder 4.
The test result of nano zirconium oxide powder is as shown in table 1.
The test result of each nano zirconium oxide powder of table 1
| Powder sample | Morphology microstructure | Tetragonal proportion, % | Monoclinic phase proportion, % | Median size, nm | Specific surface area, m 2/g |
| 1 | Sub-circular | 4 | 96 | 7.8 | 180.0 |
| 2 | Sub-circular | 99 | 1 | 5.2 | 201.4 |
| 3 | Sub-circular | 93 | 7 | 6.3 | 172.5 |
| 4 | Sub-circular | 93 | 7 | 15.4 | 85.2 |
The liquefied ammonia existed with subcritical state effectively can replace powder and show and the water in duct, reduce the reunion between powder, and make duct can not the avalanche because of removing of moisture in drying process, improve the order in duct in roasting process, be conducive to the raising of this powder specific surface, found by above experimental data, when the temperature of subcritical fluids drying process medium liquefied ammonia reaches more than 50 DEG C (corresponding pressure >0.6MPa), the specific surface area >170m of prepared nano zircite
2/ g, median size <10nm, best effect can be reached, consider the accessibility of product quality and operation, the temperature range of subcritical fluids drying process medium liquefied ammonia is preferably 50 ~ 80 DEG C, and pressure is corresponding vapour pressure, and solvent load is 1 ~ 2 times of handled quality of material, treatment time is 30 ~ 100min, and number of processes is 2 ~ 3 times.
Above-mentioned colloidal precipitation of hydroxide is separated by ceramic membrane when washing, isolate solid matter and most of liquid phase substance, then in solid matter, add pure water again, again iterate through ceramic membrane separation, until can't detect chlorion with Silver Nitrate, complete the elimination of chlorion.After processing containing solvent precipitation of hydroxide through decompression gasification, vacuum desolvation, namely obtain dry precipitation of hydroxide, finally pulverize and namely obtain Zirconium powder.
The foregoing is only section Example of the present invention, not any pro forma restriction is done to the present invention; The those of ordinary skill of all industry, all can implement the present invention program by the above; But, all technician being familiar with the industry, do not departing within the scope of technical solution of the present invention, when utilizing disclosed above technology contents, and some equivalent variations adjusting, modify and develop of making, be Equivalent embodiments of the present invention, simultaneously, all substantial technological according to the present invention are to adjustment, the modification of any equivalent variations done by above embodiment and develop, and all still belong in the scope of technical scheme of the present invention.
Claims (2)
1. a high dispersion nanometer oxide zirconium raw powder's production technology, in the aqueous solution containing zirconates, add alkaline precipitating agent obtain colloidal precipitation of hydroxide, again successively through filtering, washing and dehydration obtain dry hydrogen oxide precipitation, calcine in High Temperature Furnaces Heating Apparatus after dry hydrogen oxide precipitation is pulverized, finally obtain Zirconium powder, it is characterized in that: in the process of described dehydration, adopt the drying mode that subcritical fluids is dewatered, the drying mode of described subcritical fluids dehydration take liquefied ammonia as medium, at 50 ~ 80 DEG C of temperature, vacuumize pressure and pH value under 8.8 ~ 9.2 states, by the moisture removal in precipitation of hydroxide, the pressure of the drying mode medium liquefied ammonia of described subcritical fluids dehydration is corresponding vapour pressure, and solvent load is 1 ~ 2 times of handled quality of material, and the treatment time is 30 ~ 100min, and number of processes is 2 ~ 3 times, after processing containing solvent precipitation of hydroxide through decompression gasification, vacuum desolvation, namely obtain dry precipitation of hydroxide.
2. a kind of high dispersion nanometer oxide zirconium raw powder's production technology according to claim 1, is characterized in that: before adding alkaline precipitating agent, first adds crystal phase stablizer in the aqueous solution containing zirconates.
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| CN105621480B (en) * | 2016-01-25 | 2017-10-17 | 大连理工大学 | A kind of method that use low temperature calcination zirconium colloidal sol prepares Zirconium dioxide nano powder |
| CN107364884B (en) * | 2017-08-24 | 2019-05-14 | 江苏思麦尔生命科技有限公司 | A kind of nano zirconium oxide powder preparation method |
| CN108383157A (en) * | 2018-03-06 | 2018-08-10 | 三祥新材股份有限公司 | A kind of preparation method of nano zircite |
| CN112429771B (en) * | 2020-11-23 | 2021-06-11 | 山东国瓷功能材料股份有限公司 | Nano zirconium oxide powder, preparation method thereof, dispersion liquid obtained by preparation method and optical film |
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