CN1334243A - Process for prepairng granularity controllable nm-class zirconium oxide - Google Patents
Process for prepairng granularity controllable nm-class zirconium oxide Download PDFInfo
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Abstract
A process for preparing nm-class zirconium oxide with controllable size (less than 30 nm) includes preparing two portions of microsuspension containing non-ionic surfactant, n-hexanol, cyclohexane and zirconium salt solution or amminia water, mixing, hydrolysis reaction, centrifuging or filtering, washing with alclohol and water several times, drying and calcining. It features that its size can be controlled by controlling the content of zirconium solution or ammonia water, the ratio of water to surfactant and reaction temp.
Description
Technical field
The invention belongs to technical field of nano material, specially refer to a kind of preparation method of nano zircite of controllable size.
Background technology
Nano zircite can be used as chemical sensor, high-performance ceramic.In recent years, zirconium white is used as heterogeneous catalyst or adsorbing agent carrier also receives great concern.The preparation method of nano zircite has the precipitator method (Stichert W, Schuth F, J.Catal. usually, 1998,174:242), sol-gel method (Ward D A, Ko E I, J.Catal.1995,157:321), hydrothermal synthesis method (Tani E, Yoshimura M, Somiya S, 11) and the cracking process of organic compound (Chraska T J.Am.Ceram.Soc.1983,66 (1):, King A H, Berndt C C, Mater.Sci.Eng.A, 2000,286:169) etc.Usually, the liquid phase method easy handling, but usually cause the reunion of particle easily.
HJ Si Tezeer and W Hess (Chinese patent number of patent application: 97111560, publication number: 1169958) once report is dissolved in a kind of free from chloride zirconium compounds in formic acid and the water mixture, pass through spraying drying then, remove volatile constituent, in air, calcine the Zirconium dioxide powder that finally obtains then.This product is hollow spherical, and external diameter is 5～20 μ m, and wall thickness is approximately 1 μ m.The Zirconia particles of this patent preparation is bigger, belongs to micron-sized particle.
(Chinese patent number of patent applications: 90102519 such as Beatrice Mi Xieer and card Er Moximan, publication number: 1046879, Granted publication number: 1021689) also reported by prepare zirconium hydroxide and titanium, tantalum and the oxyhydroxide and/or the oxide compound of magnesium, aluminium, scandium, yttrium and rare earth in case of necessity with coprecipitation method in the aqueous solution, drying and roasting obtain the sintered zirconic composite oxides powder that contains again.They point out the material of hydrolysis sensitivity such as TiCl
4Can add in the Zirconium oxide powder by means of the mode that adds polyvalent alcohols such as ethylene glycol.
Above-mentioned patented method is the precipitator method, and the gained particle diameter is all in the micro-meter scale size.People such as Ramamurthl (J.Am.Ceram.Soc, 1990,73 (9): 2760) once ammonia is fed the milk sap of the water/Tween-80/ dimethylbenzene contain Zircosol ZN, prepare the Zirconia particles of several nanometers.The transmission electron microscope results of this product shows that particle agglomeration is comparatively serious, and particle size distribution is irregular.In addition, this method requires to use a large amount of gaseous ammonias, reveals easily, has bigger toxicity.(J.Colloid Interface Sci. such as Fang, 1999,212:242) adopting cats product cetyl trimethylammonium bromide (CTAB), is raw material with basic zirconium chloride and Yttrium trinitrate, has prepared the mixed oxide of zirconium and yttrium in the microemulsion system that CTAB/ n-hexyl alcohol/water is formed.The particle of this product is bigger, in 30～70nm scope.
Summary of the invention
The objective of the invention is for overcoming the weak point of prior art, a kind of method for preparing the controlled nano zircite of particle diameter is proposed, contain microemulsion and a kind of microemulsion that contains ammoniacal liquor of zirconates by certain, the reaction that is hydrolyzed in nano-reactor under controlled conditions can obtain the zirconium white particulate of the controlled amount of different-grain diameter.Simultaneously, in preparation process by adding yttrium oxide, calcium oxide, magnesium oxide and manganese oxide etc., can controlled oxidation zirconium crystal formation, obtain stable tetragonal phase zircite.
The present invention proposes a kind of method for preparing the controlled nano zircite of particle diameter, may further comprise the steps:
The first step: at first prepare the stable microemulsion liquid that contains the stable microemulsion liquid of zirconates and contain ammoniacal liquor; This process is that a kind of soluble zirconium salts solution and ammoniacal liquor are joined respectively in two portions of identical mixed solutions of being made up of a kind of nonionogenic tenside, cosurfactant n-hexyl alcohol and oil phase hexanaphthene, the volume ratio of each component is a water in this mixed solution: nonionogenic tenside: n-hexyl alcohol: hexanaphthene=1: x: y: z, wherein x is between 2～8, y is between 0～4, z continues stirring until clarification and can obtain the stable microemulsion liquid that contains the stable microemulsion liquid of zirconates and contain ammoniacal liquor respectively between 10～40;
Second step: the microemulsion that will contain the solubility zirconates directly mixes with the microemulsion equal-volume that contains ammoniacal liquor, according to predefined concentration of reactants and temperature of reaction, carries out the micro emulsion precipitin reaction; The shape mixed solution that obtains being translucent, leave standstill for some time after, demixing phenomenon is arranged, the upper strata is a clear liquid, lower floor is that fine particle is piled up the zirconium hydroxide white precipitate that forms;
The 3rd step of the present invention is for adopting vacuum-evaporation, lyophilize, super centrifugal and sucking filtering etc. usually to above-mentioned sedimentary solid-liquid separation.Several method below having adopted among the present invention: (1) evaporation drying, the throw out that is about to react gained obtains white or light yellow smectic thing with the water-bath oven dry at a certain temperature.(2) centrifugation, being about to reacted mixed solution is 5000～12000 rev/mins with rotating speed on whizzer, continues for some time, and has tangible layering, and the upper strata is the water white transparency clear liquid, and lower floor is the translucent solid of frozen glue shape oyster white.Then, with organic reagent and deionized water wash gained frozen glue shape materials such as methyl alcohol, water, acetone, dry with water-bath more earlier.(3) reflux is about to reacted liquid-phase system and carries out reflux, and the reflux time is 1～5 hour, obtains pulverulent solids through filtration and drying again.
The 4th step of the present invention is that above-mentioned separated product is carried out calcination process, above-mentioned solid sediment is dry earlier, in nitrogen, press the intensification digit rate of 5～10 ℃/min then, be heated to 90 ℃ to 120 ℃ and remove most moisture and volatile organic matter, continue to be heated to 200 ℃ to 250 ℃ and kept 1 to 3 hour then, nitrogen changed make oxygen, further remove remaining organism; At last,, keep oxygen atmosphere, remove the charcoal particle that organic matter carbonizing forms, thereby obtain final nano zirconium oxide powder at 400～600 ℃.
The present invention also proposes a kind of method for preparing the controlled nano composite oxides zirconium of particle diameter, it is identical with the method for the nano zircite that above-mentioned preparation single particle size is controlled that its step is basic, and difference is: the formulations prepared from solutions stable microemulsion liquid of the mixing solutions replacement single soluble zirconates of one or more inorganic salt such as, calcium violent with containing, magnesium or yttrium and solubility zirconates.The molar ratio of said solubility zirconates and said one or more inorganic salt is 1: (0～0.4).
The present invention can choose sample segment, records the specific surface area of sample, the granular size by the transmission electron microscope observing samples and the crystalline phase of investigating sample with X-ray diffraction by nitrogen adsorption.
The concrete grammar of the preparation of zirconium white particulate of the present invention comprises following several key parts.In the above-mentioned the first step, used tensio-active agent can be nonionogenic tensides such as TritonX-100, Tween-20, Span-80.Used zirconates can be basic zirconium chloride, Zircosol ZN or other solubility zirconates.In second step, control reaction temperature generally between 15 ℃ to 65 ℃, is preferably between 25 ℃ to 40 ℃; The concentration of said ammoniacal liquor is between 5～15 mol/l; The concentration of zirconates is between 0.1～2.0mol/l; Solid-liquid separation preferably adopts sucking filtering and centrifugation in the 3rd step.Revolution used during centrifugation can be 5000～12000 rev/mins, is generally 7000～8000 rev/mins, and centrifugation time is 10～30 minutes.In the 4th step, can remove organism in the sample by roasting, wherein roasting speed and final calcination temperature are very big to the crystal formation influence of sample.Temperature rise rate generally is controlled at 1～20 ℃/min, is preferably in 5～10 ℃/min, and final maturing temperature is decided by specifically to use desired crystalline phase.
Characteristics of the present invention: the granular size of the general precipitator method is difficult to control, and it is also irregular to distribute.The present invention by controlling the reunion that reaction conditions not only can reduce particle, can also obtain the nano oxidized particulate zirconia that different-grain diameter is big or small and be evenly distributed in the microemulsion system that a kind of nonionogenic tenside/water is formed.The size of final nano level zirconium white particulate is mainly by following condition control in the micro emulsion precipitin reaction process, i.e. the mode of the concentration of ammoniacal liquor, temperature of reaction, sedimentary separation method and sedimentary drying and roasting etc. in the concentration of zirconates, the microemulsion in the ratio of each component, the microemulsion in the microemulsion.The characteristics of present method are can obtain median size size and be several nano zircites to 30nm by controlling above-mentioned reaction conditions, and its specific surface area is tens to 300m
2/ g.The Zirconium oxide powder or the compound zirconia powder of this method preparation can be used as specific function pottery, gas sensor, catalyzer or support of the catalyst and fields such as sorbent material or adsorbing agent carrier.
Description of drawings:
Fig. 1 is the transmission electron microscope picture of zirconia products prepared in the present embodiment 6.
The specific embodiment
Embodiment 1
At first, option table surface-active agent, cosurfactant and oil phase are respectively TritonX-100, n-hexyl alcohol, ring Hexane is in following water and the ratio of organic phase, respectively with 0.8mol/l zirconium nitrate solution and 15mol/l ammoniacal liquor Join in organic mixed solution, be mixed with two parts of microemulsions, making wherein, the volume ratio of each component is water: TritonX-100: n-hexyl alcohol: cyclohexane=1: 2.1: 2.7: 15. Then, under 25 ℃, two parts of microemulsions that obtain are being swashed Mix under the strong stirring condition, and continue to stir 1 hour. With the subnatant centrifugation in the liquid-phase system, institute Be 9000 rev/mins with revolution, the duration is 30 minutes. Washing several times with methyl alcohol, water, acetone respectively, what obtain consolidates Body after drying, after 450 ℃ of roastings, recording its specific area is 74.3m2/ g, corresponding average grain diameter is 13.6nm.
Embodiment 2
The control reaction temperature is 50 ℃ in embodiment 1, and the sample that obtains records its specific area and is 85.6m through after the same processing2/ g, corresponding Average Particle Diameters is 11.8nm.
Embodiment 3
The control reaction temperature is 63 ℃ in embodiment 1, and the sample that obtains records its specific area and is 53.7m through after the same processing2/ g, corresponding Average Particle Diameters is 18.8nm.
Embodiment 4
In embodiment 1, replace TritonX-100 with surfactant Tween-20, carry out same experiment, obtain Zirconium oxide powder, after 450 ℃ of calcination process, record its specific area and be 67.4m2/ g, corresponding average particle The footpath size is 15.1nm.
Embodiment 5
In embodiment 1, replace TritonX-100 with surfactant Span-80, carry out same experiment, obtain Zirconium oxide powder, after 450 ℃ of calcination process, record its specific area and be 60.4m2/ g, corresponding average grain diameter Size is 16.8nm.
Embodiment 6
In embodiment 1, replace zirconium nitrate with basic zirconium chloride, and the concentration of getting basic zirconium chloride is 1.0mol/l, and the concentration of ammoniacal liquor is 15mol/l, and the volume ratio of each component is water: TritonX-100 in the hierarchy of control: n-hexyl alcohol: cyclohexane=1: 6.4: 2.7: 20,25 ℃ of lower reactions two hours, behind reflux heating, centrifugation obtains solia particle, equally after 450 ℃ of calcination process, record its specific area and be 185m2/ g, corresponding Average Particle Diameters is 5.6nm. Transmission electron microscope is surveyed Get its particle size in 4.0 ± 1.0 scopes, particle size distribution is very even, as shown in Figure 1.
Embodiment 7
In embodiment 1, replace zirconium nitrate with basic zirconium chloride, and the concentration of getting basic zirconium chloride is 0.4mol/l, and the concentration of ammoniacal liquor is 9mol/l, and the volume ratio of each component is water: TritonX-100 in the hierarchy of control: n-hexyl alcohol: cyclohexane=1: 2.1: 2.7: 32,25 ℃ of lower reactions two hours, behind reflux heating, centrifugation obtains solia particle, equally after 450 ℃ of calcination process, record its specific area and be 117m2/ g, corresponding Average Particle Diameters is 8.7nm.
Embodiment 8
In embodiment 7, be that 1: 0.2 basic zirconium chloride and the mixed aqueous solution of manganese nitrate replace single with mol ratio The microemulsion that makes of zirconium oxychloride solution, with the microemulsion of ammoniacal liquor, under vigorous stirring, mix again, it is light brown that system is Red. Then, with this system reflux heating after 2 hours, filter, and with ethanol and deionized water washing precipitation, again Gained is deposited in 100 ℃ of air dryings, removes residual moisture and organic matter 450 ℃ of lower roastings, obtain like this MnO2/ZrO
2Sample, recording its specific area is 250m2/ g, corresponding Average Particle Diameters is 4.1nm.
X-ray diffraction shows that this compound is initially unformed, and behind the interpolation manganese oxide, it is single being heated to 600 ℃ Tetragonal. By comparison, the sample that does not add manganese oxide namely begins to occur tetragonal phase through 450 ℃ of roastings after 3 hours With a small amount of monocline crystalline phase, along with sintering temperature is promoted to 600 ℃, the monocline crystalline phase increases. Show that the interpolation manganese oxide is passable Stop the appearance of high temperature monocline crystalline phase.
Embodiment 9
In embodiment 8, be 1: 0.05: 0.3 basic zirconium chloride with mol ratio: yttrium nitrate: the mixed aqueous solution of magnesium nitrate replaces the mixed aqueous solution of basic zirconium chloride and manganese nitrate to make microemulsion, carry out same experiment, the Y that obtains like this2O
3/MgO/ZrO
2Sample, recording its specific area is 240m2/ g, corresponding Average Particle Diameters is 4.3nm.
Claims (10)
1, a kind of method for preparing the controlled nano zircite of particle diameter may further comprise the steps:
1) at first prepares the stable microemulsion liquid that contains the stable microemulsion liquid of zirconates and contain ammoniacal liquor; This process is that a kind of soluble zirconium salts solution and ammoniacal liquor are joined respectively in two portions of identical mixed solutions of being made up of a kind of nonionogenic tenside, cosurfactant n-hexyl alcohol and oil phase hexanaphthene, the volume ratio of each component is a water in this mixed solution: nonionogenic tenside: n-hexyl alcohol: hexanaphthene=1: x: y: z, wherein x is between 2～8, y is between 0～4, z continues stirring until clarification and can obtain the stable microemulsion liquid that contains the stable microemulsion liquid of zirconates and contain ammoniacal liquor respectively between 10～40;
2) microemulsion that will contain the solubility zirconates directly mixes with the microemulsion equal-volume that contains ammoniacal liquor, according to predefined concentration of reactants and temperature of reaction, carries out the micro emulsion precipitin reaction; The shape mixed solution that obtains being translucent, leave standstill for some time after, demixing phenomenon is arranged, the upper strata is a clear liquid, lower floor is that fine particle is piled up the zirconium hydroxide white precipitate that forms;
3) above-mentioned precipitation is adopted solid-liquid separation; This solid-liquid separating method adopts any method among vacuum-evaporation, lyophilize, the super centrifugal and sucking filtering, obtains solid sediment;
4) above-mentioned solid sediment is dry earlier, in nitrogen, press the intensification digit rate of 5～10 ℃/min then, be heated to 90 ℃ to 120 ℃ and remove most moisture and volatile organic matter, continue to be heated to 200 ℃ to 250 ℃ and kept 1 to 3 hour then, nitrogen changed make oxygen, further remove remaining organism; At last,, keep oxygen atmosphere, remove the charcoal particle that organic matter carbonizing forms, thereby obtain final nano zirconium oxide powder at 400～600 ℃.
As the method for the controlled nano zircite of the preparation particle diameter of right 1, it is characterized in that 2, said nonionogenic tenside can be TritonX-100 (C
34H
62O
11, molecular weight 646.86), among Span-80, the Tween-20 any.
As the method for the controlled nano zircite of the preparation particle diameter of right 1, it is characterized in that 3, said zirconates is a kind of of basic zirconium chloride or zirconium nitrate.
As the method for the controlled nano zircite of the preparation particle diameter of right 1, it is characterized in that 4, the separation method of said solid-liquid is the evaporation drying method, the throw out that is about to react gained obtains the smectic thing with the water-bath oven dry at a certain temperature.
5, as the method for the controlled nano zircite of the preparation particle diameter of right 1, it is characterized in that the separation method of said solid-liquid is a centrifugal separation, being about to reacted mixed solution is 5000～12000 rev/mins with rotating speed on whizzer, continue for some time, tangible layering occurs; The upper strata is the water white transparency clear liquid, and lower floor is the translucent solid of frozen glue shape oyster white, so uses organic reagent and deionized water wash gained solid matters such as methyl alcohol, water, acetone, can obtain solid sediment with the water-bath oven dry again.
6, as the method for the controlled nano zircite of the preparation particle diameter of right 1, it is characterized in that the separation method of said solid-liquid is the reflux method, be about to reacted liquid-phase system and carried out reflux 1～5 hour, then, can obtain solid sediment through the funnel vacuumizing filtration again.
As the method for the controlled nano zircite of the preparation particle diameter of right 1, it is characterized in that 7, said temperature of reaction generally between 15 ℃ to 65 ℃, is preferably between 25 ℃ to 40 ℃.
As the method for the controlled nano zircite of the preparation particle diameter of right 1, it is characterized in that 8, the concentration of said ammoniacal liquor is between 5～15mol/l; The concentration of zirconates is between 0.1～2.0mol/l.
9, a kind of method for preparing the controlled nano composite oxides zirconium of particle diameter may further comprise the steps:
1) at first prepares the stable microemulsion liquid that contains the stable microemulsion liquid of zirconates and contain ammoniacal liquor; This process is violent with containing, calcium, the mixing solutions of one or more inorganic salt such as magnesium or yttrium and solubility zirconates, and ammoniacal liquor join respectively two parts identical by a kind of nonionogenic tenside, in the mixed solution that cosurfactant n-hexyl alcohol and oil phase hexanaphthene are formed, the volume ratio of each component is a water in this mixed solution: nonionogenic tenside: n-hexyl alcohol: hexanaphthene=1: x: y: z, wherein x is between 2～8, y is between 0～4, z continues stirring until clarification and can obtain the stable microemulsion liquid that contains the stable microemulsion liquid of zirconates and contain ammoniacal liquor respectively between 10～40;
2) microemulsion that will contain described solubility zirconates directly mixes with the microemulsion equal-volume that contains ammoniacal liquor, according to predefined concentration of reactants and temperature of reaction, carries out the micro emulsion precipitin reaction; The shape mixed solution that obtains being translucent, leave standstill for some time after, demixing phenomenon is arranged, the upper strata is a clear liquid, lower floor is that fine particle is piled up the hydrogeneous zirconic white precipitate that forms;
3) above-mentioned precipitation is adopted solid-liquid separation; This solid-liquid separating method adopts any method among vacuum-evaporation, lyophilize, the super centrifugal and sucking filtering, obtains solid sediment;
4) above-mentioned solid sediment is dry earlier, in nitrogen, press the intensification digit rate of 5～10 ℃/min then, be heated to 90 ℃ to 120 ℃ and remove most moisture and volatile organic matter, continue to be heated to 200 ℃ to 250 ℃ and kept 1 to 3 hour then, nitrogen changed make oxygen, further remove remaining organism; At last,, keep oxygen atmosphere, remove the charcoal particle that organic matter carbonizing forms at 400～600 ℃, thus the composite Nano Zirconium oxide powder that the crystal formation of the modification that obtains can be controlled.
10, the method for the controlled nano composite oxides zirconium of preparation particle diameter as claimed in claim 9 is characterized in that the molar ratio of said solubility zirconates and said one or more inorganic salt is 1: (0～0.4).
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