CN105585047A - Preparation method of monoclinic-phase nano zirconium dioxide, and the monoclinic-phase nano zirconium dioxide prepared therethrough - Google Patents
Preparation method of monoclinic-phase nano zirconium dioxide, and the monoclinic-phase nano zirconium dioxide prepared therethrough Download PDFInfo
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- CN105585047A CN105585047A CN201410577953.4A CN201410577953A CN105585047A CN 105585047 A CN105585047 A CN 105585047A CN 201410577953 A CN201410577953 A CN 201410577953A CN 105585047 A CN105585047 A CN 105585047A
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Abstract
The invention discloses a preparation method of monoclinic-phase nano zirconium dioxide, and the monoclinic-phase nano zirconium dioxide prepared therethrough. The preparation method includes the following steps: 1) contacting a solid mixture containing a zirconium source and a solid organic amine with water vapor in a sealed container to prepare zirconium hydroxide, the temperature of the water vapor being 100-250 DEG C; and 2) drying and roasting the zirconium hydroxide to prepare the monoclinic-phase nano zirconium dioxide. The method improves the pore structure of the zirconium dioxide and increases yield of the zirconium dioxide, is free of product separation and reduces wastewater treatment.
Description
Technical field
The present invention relates to a kind of preparation method of monoclinic phase nano zirconium dioxide and prepare with the methodMonoclinic phase nano zirconium dioxide, particularly, relates to a kind of that the solid that contains zirconium source and SOLID ORGANIC amine is mixedThereby contacting to react with water vapour vapour solid phase, compound prepares the method for nanoscale monoclinic phase zirconium dioxide,And the nanoscale monoclinic phase zirconium dioxide being prepared by the method.
Background technology
Zirconium dioxide is a kind of oxide with extensive use. For example, zirconium dioxide has good resistance toHigh temperature, corrosion-resistant and heat-insulating property, be just applied to melting glass as refractory material a long time agoThe every field such as glass, iron and steel smelting. Zirconium dioxide is also a kind of good oxidesolid electrolyte material,Aspect special cermacis and functional material, having broad application prospects. In addition, due to zirconium dioxide surfaceHave acidity, alkalescence, oxidisability and reproducibility, therefore it both can be used as catalyst, also can be used as simultaneouslyCatalyst carrier. Zirconium dioxide or p-type semi-conducting material, be easy to produce oxygen vacancies, as catalystCarrier can produce stronger interaction with active component. Simultaneously due to the mechanical strength of zirconium dioxideCan also serve as the structural promoter of catalyst, at the aspect such as hydrogenation catalyst and solid superacid as catalyst well,All be with a wide range of applications.
But with γ-Al2O3, silica gel compares, the specific area of zirconium dioxide is lower, has limited it and has urgedThe application in change field. To separate for obtaining the zirconium dioxide of high-specific surface area, preparing nano zirconium dioxide crystalCertainly one of approach of this problem. Traditional zirconium dioxide preparation method mainly contains the precipitation method, sol-gelMethod, hydro-thermal method, reverse micelle method etc. Above method all relates to liquid phase reactor, and result causes synthesizedZirconium dioxide crystalline size is less, more difficultly from synthetic system, separates, and causes the production cost of zirconium dioxideVery high, waste water is more simultaneously.
Therefore, need a kind of production method of zirconium dioxide, solve difficult point of prior art zirconium dioxide crystalFrom problem, obtain the zirconium dioxide of high-specific surface area and yield and the crystallization that improves zirconium dioxide crystalDegree.
Summary of the invention
The object of the invention is the defect in order to overcome prior art, a kind of monoclinic phase nanometer titanium dioxide is providedThe preparation method of zirconium and the monoclinic phase nano zirconium dioxide of preparing with the method.
To achieve these goals, the invention provides a kind of preparation method of monoclinic phase nano zirconium dioxide,The method comprises: (1) by the solid mixture that contains zirconium source and SOLID ORGANIC amine and water vapour in airtight appearanceIn device, contact, obtain zirconium hydroxide; The temperature of water vapour is 100-250 DEG C; (2) zirconium hydroxide is enteredRow is dried and roasting, obtains monoclinic phase nano zirconium dioxide.
The present invention also provides the zirconium dioxide being prepared by method provided by the invention, this zirconium dioxideParticle diameter be 3-20nm, specific area is 80-150m2/ g, pore volume is 0.1-0.4cm3/ g, crystalline phaseFor monoclinic phase.
Method provided by the invention adopts the realization that contacts of water vapour and solid reactant to prepare monoclinic phase and receiveRice zirconium dioxide, and do not need product to separate, can improve the pore structure of zirconium dioxide, improve twoThe yield of crystal of zirconium oxide; And water consumption is little, reduce wastewater treatment.
Other features and advantages of the present invention are described in detail the detailed description of the invention part subsequently.
Brief description of the drawings
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for description, withDetailed description of the invention one is below used from explanation the present invention, but is not construed as limiting the invention. ?In accompanying drawing:
Fig. 1 is the enforcement schematic diagram of a kind of preferred embodiment of the present invention.
Fig. 2 is the XRD spectra of the monoclinic phase nano zirconium dioxide prepared of embodiment 1.
Description of reference numerals
1, Pressure vessel 2, reaction mass 3, porous screen cloth
4, water
Detailed description of the invention
Below the specific embodiment of the present invention is elaborated. Should be understood that, retouch in this placeThe detailed description of the invention of stating only, for description and interpretation the present invention, is not limited to the present invention.
The preparation method who the invention provides a kind of monoclinic phase nano zirconium dioxide, the method comprises: (1) willThe solid mixture that contains zirconium source and SOLID ORGANIC amine contacts in closed container with water vapour, obtains hydrogen-oxygenChange zirconium; The temperature of water vapour is 100-250 DEG C; Preferably, the temperature of water vapour is 100-200 DEG C; (2)Zirconium hydroxide is dried and roasting, obtains monoclinic phase nano zirconium dioxide.
In the present invention, this method is implemented in closed container, and reaction pressure is wherein corresponding water vapourThe water saturation vapour pressure of temperature.
According to the present invention, the consumption of described zirconium source and described SOLID ORGANIC amine is prepared zirconium dioxide as long as meetReaction needed. Under preferable case, the mol ratio of described zirconium source and SOLID ORGANIC amine is 1:1-10.
According to the present invention, water vapour provides the water of gaseous state to participate in described solid mixture is reacted, shapeBecome the presoma of zirconium dioxide, i.e. zirconium hydroxide. The amount of water vapour meets reaction needed. The present inventionIn the method providing, ensure under above-mentioned reaction temperature, at the temperature of water vapour with described solids mixingThe amount of the water vapour of thing contact, can make zirconium source change zirconium hydroxide into completely. Preferably, the consumption of waterFor being enough to generate saturated vapor in the course of reaction of zirconium hydroxide is changed in above-mentioned zirconium source into. Preferably, instituteThe mol ratio of stating solid mixture and water is not more than 1:10, and is not less than 1:100; At 100-250 DEG C and excellentSelect under 100-200 DEG C of condition, steam turns to water vapour, occurs with described zirconium source and described SOLID ORGANIC amineVapour solid phase contacts and reacts.
According to the present invention, described zirconium source is not particularly limited, and under preferable case, described zirconium source is in stepSuddenly described in (1), under the condition of contact, can change the material of zirconium hydroxide into; Preferably, described zirconiumSource is at least one in zirconyl nitrate, zirconium oxychloride, zirconyl carbonate and zirconium nitrate
According to the present invention, described SOLID ORGANIC amine is not particularly limited, under preferable case, and described solidOrganic amine is urea and/or hexamethylenetetramine.
In the present invention, the particle diameter of the solid mixture that contains described zirconium source and SOLID ORGANIC amine can be150-300μm。
Method provided by the invention, for example taking zirconyl nitrate as zirconium source, is mixed into taking urea as SOLID ORGANIC amine, under water vapour exists, there is following course of reaction in solid mixture:
4ZrO(NO3)2+6H2O＝Zr4O2(OH)8(NO3)4+4HNO3
Zr4O2(OH)8(NO3)4+2CO(NH2)2+8H2O＝4Zr(OH)4+4NH4NO3+2CO2
Water vapour contacts with urea generation vapour solid phase with zirconyl nitrate, and zirconates turns through hydrolysis and through urea precipitationTurn to zirconium hydroxide crystal; Then zirconium hydroxide is converted into zirconium dioxide under high-temperature roasting:
Zr(OH)4＝ZrO2+2H2O
The whole process of method of the present invention does not have liquid phase to participate in.
According to the present invention, the condition of preparing zirconium dioxide is not particularly limited, and meets reaction needed, obtainsObtain monoclinic phase zirconium dioxide. Under preferable case, the time of described contact is 1-50h; Described dryTemperature be 100-120 DEG C, the described dry time is 10-14h, the temperature of described roasting is 400-600DEG C, the time of described roasting is 2-6h.
According to the present invention, a kind of method of preferably preparing zirconium dioxide is specially: as shown in Figure 1, and instituteState closed container and comprise porous screen cloth, will contain solid mixture and the water vapour of zirconium source and SOLID ORGANIC amineThe mode of contact is included in closed container and fills water, will contain the solids mixing of zirconium source and SOLID ORGANIC amineThing is placed on porous screen cloth, and porous screen cloth has on the water surface and between the lower surface of porous screen cloth and the water surfaceGap, then heating, makes the water in closed container form water vapour, and water vapour, through porous screen cloth, arrivesReach the solid mixture surface of containing zirconium source and SOLID ORGANIC amine being positioned on porous screen cloth. Described airtight appearanceDevice can be Pressure vessel.
According to the present invention, described porous screen cloth can be not particularly limited, and the aperture of porous screen cloth is greater thanThe particle diameter of solid mixture, does not make solid mixture fall. Under preferable case, described porousThe porosity of screen cloth is 4000-250000 hole/cm2, the aperture of described porous screen cloth is 20-150 μ m.
The zirconium dioxide that the present invention also provides method provided by the invention to prepare, this zirconium dioxideParticle diameter is 3-20nm, and specific area is 80-150m2/ g, pore volume is 0.1-0.4cm3/ g, crystalline phase is singleMonoclinic phase.
Below will describe the present invention by embodiment.
In following examples, zirconium dioxide product adopts JEOL company by transmission electron microscope methodThe determination of transmission electron microscopy particle diameter of JEM-ARM200F model;
Adopt the X-of the D/max-2600/pc of Rigaku company model to penetrate by X-ray powder diffraction methodLine diffractometer is measured the XRD spectra of product, with standard spectrogram (PDF2-2004) comparison, is defined as listMonoclinic phase ZrO2；
Adopt the specific surface of the tristarII3020-M of Micromeritics company model to divide by nitrogen adsorption methodAnalyse the pore structure of instrument Instrument measuring product;
The yield of product crystal is calculated as follows:
Monoclinic phase ZrO2ZrO in yield=product quality/raw material zirconium source of crystal2Content × 100%.
Embodiment 1
As shown in Figure 1, in Pressure vessel, pack the water of 20g into, by the ZrO (NO of 20g3)2·2H2O(particle diameter is that m) (particle diameter is that 300 μ m) mix to 150 μ, puts with the urea of 4.5gOn screen cloth, (porosity is 4000 holes/cm2, aperture be 150 μ m), more than being placed in the water surface, do not contactThe water surface.
By airtight Pressure vessel heating, at 180 DEG C, keep 12h. Take out the product powder on screen cloth,Dry 12h at 120 DEG C, roasting 2h at 450 DEG C, obtains 10.1g product ZR-1.
The particle diameter of measuring ZR-1 is 20nm;
Measure the XRD spectra (Fig. 2) of ZR-1, compare and be defined as monoclinic phase ZrO with standard spectrogram2BrilliantBody;
The pore structure of measuring ZR-1, specific area is 80m2/ g, pore volume is 0.40cm3/g；
Monoclinic phase ZrO2The yield of crystal is 95%.
Embodiment 2
As shown in Figure 1, in Pressure vessel, pack the water of 20g into, by the ZrO (NO of 20g3)2·2H2OMix with the urea of 45g, be put in that on screen cloth, (porosity is 250000 holes/cm2, aperture be 20 μ m),More than being placed in the water surface, do not contact the water surface.
By airtight Pressure vessel heating, at 250 DEG C, keep 1h. Take out the product powder on screen cloth,Dry 10h at 100 DEG C, roasting 6h at 400 DEG C, obtains 10.3g product ZR-2.
The particle diameter of measuring ZR-2 is 10nm;
Measure the XRD spectra of ZR-2, compare and be defined as monoclinic phase ZrO with standard spectrogram2Crystal;
The pore structure of measuring ZR-2, specific area is 100m2/ g, pore volume is 0.25cm3/g。
Monoclinic phase ZrO2The yield of crystal is 97%.
Embodiment 3
As shown in Figure 1, in Pressure vessel, pack the water of 20g into, by the ZrO (NO of 20g3)2·2H2OMix with the urea of 20g, be put in that on screen cloth, (porosity is 20000 holes/cm2, aperture be 70 μ m),More than being placed in the water surface, do not contact the water surface.
By airtight Pressure vessel heating, at 100 DEG C, keep 50h. Take out the product powder on screen cloth,Dry 14h at 120 DEG C, roasting 4h at 600 DEG C, obtains 10.45g product ZR-3.
The particle diameter of measuring ZR-3 is 3nm;
Measure the XRD spectra of ZR-3, compare and be defined as monoclinic phase ZrO with standard spectrogram2Crystal;
The pore structure of measuring ZR-3, specific area is 120m2/ g, pore volume is 0.1cm3/g。
Monoclinic phase ZrO2The yield of crystal is 98%.
Embodiment 4
As shown in Figure 1, in Pressure vessel, pack 20g water into, by the Zr (NO of 20g3)4·2H2O and 10gUrea mix, be put in that on screen cloth, (porosity is 20000 holes/cm2, aperture be 70 μ m), putMore than the water surface, do not contact the water surface.
By airtight Pressure vessel heating, at 150 DEG C, keep 12h. Take out the product powder on screen cloth,Dry 12h at 110 DEG C, roasting 4h at 500 DEG C, obtains 5.57g product ZR-4.
The particle diameter of measuring ZR-4 is 5nm;
Measure the XRD spectra of ZR-4, compare and be defined as monoclinic phase ZrO with standard spectrogram2Crystal;
The pore structure of measuring ZR-4, specific area is 135m2/ g, pore volume is 0.35cm3/g。
Monoclinic phase ZrO2The yield of crystal is 97%.
Embodiment 5
As shown in Figure 1, in Pressure vessel, pack 20g water into, by the Zr (NO of 20g3)4·2H2O and 15gUrea mix, be put in that on screen cloth, (porosity is 20000 holes/cm2, aperture be 70 μ m), putMore than the water surface, do not contact the water surface.
By airtight Pressure vessel heating, at 200 DEG C, keep 8h. Take out the product powder on screen cloth,Dry 10h at 120 DEG C, roasting 2h at 550 DEG C, obtains 5.63g product ZR-5.
The particle diameter of measuring ZR-5 is 5nm;
Measure the XRD spectra of ZR-5, compare and be defined as monoclinic phase ZrO with standard spectrogram2Crystal;
The pore structure of measuring ZR-5, specific area is 118m2/ g, pore volume is 0.2cm3/g。
Monoclinic phase ZrO2The yield of crystal is 98%.
Embodiment 6
As shown in Figure 1, in Pressure vessel, pack 20g water into, by the ZrOCl of 20g2·8H2O and 10gHexamethylenetetramine mix, be put in that on screen cloth, (porosity is 250000 holes/cm2, aperture is20 μ m), more than being placed in the water surface, do not contact the water surface.
By airtight Pressure vessel heating, at 250 DEG C, keep 12h. Take out the product powder on screen cloth,Dry 10h at 120 DEG C, roasting 4h at 450 DEG C, obtains 7.42g product ZR-6.
The particle diameter of measuring ZR-6 is 15nm;
Measure the XRD spectra of ZR-6, compare and be defined as monoclinic phase ZrO with standard spectrogram2Crystal;
The pore structure of measuring ZR-6, specific area is 92m2/ g, pore volume is 0.15cm3/g。
Monoclinic phase ZrO2The yield of crystal is 97%.
Embodiment 7
As shown in Figure 1, in Pressure vessel, pack 20g water into, by the ZrOCl of 20g2·8H2O and 20gHexamethylenetetramine mix, be put in that on screen cloth, (porosity is 250000 holes/cm2, aperture is20 μ m), more than being placed in the water surface, do not contact the water surface.
By airtight Pressure vessel heating, at 180 DEG C, keep 12h. Take out the product powder on screen cloth,Dry 12h at 120 DEG C, roasting 6h at 450 DEG C, obtains 7.27g product ZR-7.
The particle diameter of measuring ZR-7 is 5nm;
Measure the XRD spectra of ZR-7, compare and be defined as monoclinic phase ZrO with standard spectrogram2Crystal;
The pore structure of measuring ZR-7, specific area is 120m2/ g, pore volume is 0.38cm3/g。
Monoclinic phase ZrO2The yield of crystal is 95%.
As can be seen from the above-described embodiment, method provided by the invention can directly obtain product powder, nothingNeed that traditional preparation method's (all relating to liquid phase reactor) is necessary to be separated solid product from liquid phaseProblem, avoided that in prior art, product separation step exists with the less separation of zirconium dioxide crystalline sizeMore difficult, and the defect of generation waste water. Method provided by the invention, the zirconium dioxide product obtaining is (singleMonoclinic phase ZrO2Crystal) can there be high yield and the pore structure of improvement, as higher specific area.
Claims (10)
1. a preparation method for monoclinic phase nano zirconium dioxide, the method comprises:
(1) solid mixture and the water vapour that contain zirconium source and SOLID ORGANIC amine are connect in closed containerTouch, obtain zirconium hydroxide; The temperature of water vapour is 100-250 DEG C;
(2) zirconium hydroxide is dried and roasting, obtains monoclinic phase nano zirconium dioxide.
2. method according to claim 1, wherein, described zirconium source and SOLID ORGANIC amine moleThan being 1:1-10.
3. method according to claim 1, wherein, the temperature that reaction pressure is corresponding water vapourWater saturation vapour pressure;
The consumption of water is to be enough to generate saturated steaming in the course of reaction of zirconium hydroxide is changed in above-mentioned zirconium source intoVapour;
The time of described contact is 1-50h; Described dry temperature is 100-120 DEG C, described dryTime is 10-14h; The temperature of described roasting is 400-600 DEG C, and the time of described roasting is 2-6h.
4. according to the method described in any one in claim 1-3, wherein, described zirconium source is in stepSuddenly described in (1), under the condition of contact, can change the material of zirconium hydroxide into.
5. method according to claim 4, wherein, described zirconium source is zirconyl nitrate, oxychlorinationAt least one in zirconium, zirconyl carbonate and zirconium nitrate.
6. method according to claim 1, wherein, described SOLID ORGANIC amine is urea and/or sixMethine tetramine.
7. according to the method described in claim 1 or 3, wherein, the rubbing of described solid mixture and waterYou are than being not more than 1:10, and are not less than 1:100.
8. method according to claim 1, wherein, described closed container comprises porous screen cloth,The mode that the solid mixture that contains zirconium source and SOLID ORGANIC amine is contacted with water vapour comprises: in airtight appearanceIn device, fill water, the solid mixture that contains zirconium source and SOLID ORGANIC amine is placed on porous screen cloth to porousScreen cloth is on the water surface and gapped between the lower surface of porous screen cloth and the water surface; Then heating, makes airtightWater in container forms water vapour, and water vapour, through porous screen cloth, arrives and is positioned at containing on porous screen clothThe solid mixture surface of zirconium source and SOLID ORGANIC amine.
9. method according to claim 8, wherein, the porosity of described porous screen cloth is4000-250000 hole/cm2, the aperture of described porous screen cloth is 20-150 μ m.
10. the zirconium dioxide that in claim 1-9, the method described in any one prepares, this dioxyThe particle diameter of changing zirconium is 3-20nm, and specific area is 80-150m2/ g, pore volume is 0.1-0.4cm3/g，Crystalline phase is monoclinic phase.
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| CN108706631A (en) * | 2018-08-08 | 2018-10-26 | 景德镇陶瓷大学 | A kind of preparation method of rectangular patch monoclinic zirconia |
| CN114751451A (en) * | 2022-05-19 | 2022-07-15 | 美轲(广州)新材料股份有限公司 | Preparation method of nano zirconia |
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Address after: 100011 Beijing Dongcheng District, West Binhe Road, No. 22 Patentee after: CHINA ENERGY INVESTMENT Corp.,Ltd. Patentee after: Beijing low carbon clean energy research institute Address before: 100011 Shenhua building, 22 West Binhe Road, Dongcheng District, Beijing Patentee before: SHENHUA GROUP Corp.,Ltd. Patentee before: Beijing low carbon clean energy research institute |
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