CN106277049A - A kind of transparent nano zirconium oxide liquid dispersion and preparation method and application - Google Patents

Abstract

The invention discloses a transparent nano-zirconia liquid-phase dispersion, a preparation method and application thereof. The dispersion includes a liquid phase medium and nano zirconia particles, and the nano zirconia particles are uniformly dispersed in the liquid phase medium; the solid content of the dispersion is 1wt% to 50wt%; the nano zirconia particles The one-dimensional size is 1-12nm; the liquid phase medium is water, an organic solvent, a mixture of water-miscible organic solvent and water or a mixture of different organic solvents. The nano-zirconia in the product has high crystallinity, small particle size and uniform distribution, does not contain any surfactant, high purity, good dispersion effect, and no sedimentation after standing for ≥6 months. The product obtained by the method is directly a transparent nano-zirconia liquid-phase dispersion without any treatment, and does not need to add any substances to assist dispersion in the process. The problem of poor performance endows the product with higher application performance and a wider range of applications.

Description

A kind of transparent nano-zirconia liquid phase dispersion and its preparation method and application

technical field

The invention relates to the technical field of nanometer materials. More specifically, it relates to a liquid-phase dispersion of transparent nano-zirconia and its preparation method and application.

Background technique

Nano zirconia has the characteristics of high melting point, high boiling point, small thermal conductivity, small thermal expansion coefficient, good wear resistance, high refractive index, and excellent corrosion resistance. It can be widely used in functional ceramics, gemstone industry, catalyst industry, and piezoelectric components. , ion exchangers, solid electrolytes and environmental protection and other fields. As an electronic ceramic material, nano-zirconia can be used to manufacture filters, ultrasonic oscillators, high-temperature conductors, piezoelectric elements and solid fuel cells, etc.; as a functional ceramic material, nano-zirconia can be used to manufacture gas, temperature, sound, pressure, acceleration As well as raw materials for sensors such as humidity. Zirconia has a strong affinity for organic phosphonic acid compounds and humic acids. Using this feature, nano-zirconia can be compounded in the separation membrane for the separation, extraction and purification of some alkylphosphonic acids, and can also be used for Treatment of organic waste water. The refractive index of the material can be adjusted by using nano-zirconia, which is very valuable for optoelectronic components, optical waveguides, nonlinear optical materials, and optical sensors. The far-infrared emission characteristics of nano-zirconia make it also have certain applications in sterilization, health care and thermal barrier coatings.

As we all know, the excellent properties of many nanomaterials depend on the particle size, degree of dispersion, preparation process and other factors of nanomaterials. For nano-zirconia, which is widely used in the optical field, good dispersion performance and small and uniform particle size distribution are very important, which can directly affect the optical properties of itself and composite materials.

At present, the technology for preparing nano-zirconia powder at home and abroad is relatively mature. The common method is to use soluble zirconium salt and alkali source (such as ammonia, sodium hydroxide, potassium hydroxide, etc.) to prepare zirconium hydroxide. The obtained particles are coated with an agent, and crystalline zirconia is formed by calcining or hydrothermally. For example: Chinese patent application number is the patent of 201010218239.8, and its preparation method is to use zirconium oxychloride and sodium hydroxide that add carboxymethyl cellulose, hydroxyethyl methyl cellulose etc. Nano zirconia powder is made by chemicalization, filtration, spray drying and calcination; the patent of Chinese patent application number 200920188008.4 uses quaternary ammonium base as precipitant and modifier, and is prepared by precipitation, filtration, azeotropic drying, calcination and grinding product. The common defect of this kind of preparation method is that the produced product has serious agglomeration, large particle size, poor compatibility with other materials and poor transparency when applied to composite materials, which seriously limits the application in optics and other related fields. .

In addition, there are also methods for preparing zirconia dispersions disclosed in the prior art, for example: Chinese Patent Application No. 201180072212.5 and Chinese Patent Application No. 200980150498.7. The former uses zirconium oxychloride and alkali metal halides to hydroheat under high temperature conditions to prepare white zirconia slurry, and then strengthen acid to acidify and peptize to obtain monoclinic zirconia colloidal suspension. As we all know, zirconia is very stable, and crystallized zirconia can only be dissolved in hot concentrated hydrofluoric acid, nitric acid and sulfuric acid; this method realizes acidification by adding hydrochloric acid, etc. It can be seen that the dissolution sacrifices the incompletely crystallized zirconia, and the remaining Crystallized zirconia cores are used to reduce the particle size and achieve dispersion. The utilization rate of raw materials is low, and the sewage contains a large amount of zirconia, which is neither economical nor environmentally friendly. In addition, the preparation process is cumbersome and lengthy due to the added strong acid peptization step and long-term hydrothermal process. The latter uses zirconium oxyacetate as the source of zirconium. The raw material is expensive and economical, and additional carboxylic acids such as citric acid need to be added to stabilize the particles.

Contents of the invention

An object of the present invention is to provide a transparent nano-zirconia liquid phase dispersion. The solid content of the liquid phase dispersion is 1wt%-50wt%, the zirconia crystal particle size is small, the distribution is uniform, the one-dimensional size is 1-12nm, and the average particle size is only 6nm; in addition, the liquid phase dispersion does not contain any surface activity Stable dispersion can be achieved with only one agent, the product has high purity, good dispersion effect, no sedimentation after standing for ≥6 months, and the liquid phase dispersion can use water, organic solvent or their mixture as the dispersion medium, and has a wide range of applications.

The second object of the present invention is to provide a method for preparing a transparent nano-zirconia liquid phase dispersion. The method adopts the method of hydrolyzing inorganic zirconium salts to prepare the precursor hydrated zirconia. After washing and hydroheating, the hydrothermal product does not need any treatment, and is directly a transparent zirconia liquid phase dispersion, without adding any auxiliary materials during the process. Dispersion can solve the problems of easy agglomeration of nano-zirconia particles, poor dispersion, and poor optical properties of composite materials, thereby endowing the product with higher application performance and a wider range of applications.

The third object of the present invention is to provide an application of a transparent nano-zirconia liquid phase dispersion.

In order to achieve the above-mentioned first object, the present invention adopts the following technical solutions:

A transparent nano zirconia liquid phase dispersion, comprising a liquid phase medium and nano zirconia particles, the nano zirconia particles are uniformly dispersed in the liquid phase medium; the solid content of the dispersion is 1wt% to 50wt%; The one-dimensional size of the nano zirconia particles is 1-12nm; the liquid phase medium is water, an organic solvent, a mixture of a water-miscible organic solvent and water or a mixture of different organic solvents.

Preferably, the organic solvent is selected from one or more of the following substances: methanol, ethanol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, n-propanol, isopropanol, n-butanol, Isobutanol, acetic acid, acetonitrile, N-N dimethylformamide, acetone, aniline, dimethylsulfoxide, tetrahydrofuran, pyridine, ethyl acetate, methyl acetate, and butyl acetate. The organic solvent has relatively high polarity and low surface tension, which is beneficial to the stable dispersion of nano zirconia particles.

In the prior art, in order to control the size of nano zirconia to a small level and achieve good zirconia liquid phase dispersion, it is generally necessary to add surface modifiers, such as citric acid and other carboxylic acids, various labels silane coupling agent, etc., to ensure that the particles do not agglomerate during the preparation process (especially during the hydrothermal process), which undoubtedly increases a series of complicated processes such as surface modification and removal of excess modifiers, and modifiers The addition of will affect the performance of the product to a certain extent, and its solid content cannot reach the level of 50wt%. The present invention does not add substances to assist dispersion, and relies on the adjustment of various reaction conditions such as reaction medium, hydrothermal medium, and pH, so that the nano-zirconia particles are charged with a certain amount of positive charges, thereby polarizing the molecules of the dispersion medium with a certain polarity. And form an electric double layer structure to surround the surface of the particles, and then can be stably dispersed in the water phase, different organic phases and their mixed phases, without introducing any auxiliary substances, avoiding the traditional hydrothermal process. The problem of agglomeration between nanoparticles. After a series of parameters such as hydrothermal precursor, hydrothermal medium, hydrothermal time and hydrothermal temperature have been adjusted in large quantities, the electrical double layer of the precursor is very stable, and it can still be stable in a high temperature and high pressure hydrothermal environment. Therefore, it ensures that the particles do not agglomerate during the whole preparation process, successfully controls the particle size in a very small range, effectively improves the transparency of the dispersion, and thus greatly broadens its use range and application performance.

In order to achieve the above-mentioned second purpose, the present invention adopts the following technical solutions:

A method for preparing a transparent nano-zirconia liquid phase dispersion as described above, is characterized in that it comprises the following steps:

1) Take water, an organic solvent, a mixture of a water-miscible organic solvent and water or a mixture of different organic solvents as a solvent, and add zirconium salt thereinto to prepare a zirconium salt solution;

2) taking water, an organic solvent, a mixture of a water-miscible organic solvent and water or a mixture of different organic solvents as a solvent, adding a hydrolysis accelerator to it to prepare a hydrolysis accelerator solution;

3) mixing the zirconium salt solution and the hydrolysis accelerator solution to obtain an acidic reaction solution;

4) Aging the above acidic reaction solution, washing the aged acidic reaction solution to obtain a precursor dispersion;

5) The precursor dispersion is subjected to hydrothermal treatment to obtain the product transparent nano-zirconia liquid phase dispersion.

Preferably, in step 1), the zirconium salt is selected from one or more of the following substances: zirconium nitrate, zirconyl nitrate, zirconium oxychloride and zirconium chloride.

Preferably, in step 1), the concentration of the zirconium salt solution is 1wt%-30wt%.

More preferably, in step 1), the concentration of the zirconium salt solution is 1wt% to 15wt%;

Most preferably, in step 1), the concentration of the zirconium salt solution is 1wt%-5wt%.

Preferably, in step 1), the organic solvent is selected from one or more of the following substances: methanol, ethanol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, n-propanol, isopropanol , n-butanol, isobutanol, acetic acid, acetonitrile, acetone, dimethylsulfoxide, tetrahydrofuran, pyridine, ethyl acetate, methyl acetate, and butyl acetate. Since the present invention does not use any auxiliary dispersing substances, it does not need to consider the dissolution and reaction problems of surface modifiers and the like, thereby greatly widening the selection range of solvents.

Preferably, in step 2), the hydrolysis accelerator is selected from one or more of the following substances: potassium hydroxide, sodium hydroxide, ammonia water, triethanolamine and ethylenediamine.

Preferably, in step 2), the concentration of the hydrolysis accelerator is 0.1wt% to 20wt%,

More preferably, in step 2), the concentration of the hydrolysis accelerator is 0.1wt% to 10wt%;

Most preferably, in step 2), the concentration of the hydrolysis accelerator is 0.1wt%-5wt%.

Preferably, in step 2), the solvent is selected from one or more of the following substances: water, methanol, ethanol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, n-propanol, isopropanol Alcohol, n-butanol, isobutanol, acetonitrile, N-N dimethylformamide, acetone, aniline, dimethylsulfoxide, tetrahydrofuran, pyridine, ethyl acetate, methyl acetate and butyl acetate;

Preferably, in step 3), before mixing the hydrolysis accelerator and the zirconium salt solution, the zirconium salt solution and the hydrolysis accelerator solution need to be fully stirred evenly, and in the stirring state, the hydrolysis accelerator solution is added to the zirconium salt solution dropwise at a uniform speed. In the salt solution, the final pH value of the acidic reaction solution is controlled to be 0-7, the stirring rate is ≥300r/min, and the temperature of the adding process is 0-65°C;

Preferably, in step 3), the final pH value of the acidic reaction solution is controlled to be 0.5-6, the stirring rate is ≥500r/min, and the temperature of the addition process is 10-50°C;

More preferably, in step 3), the final pH of the acidic reaction solution is controlled to be 1-5, and the temperature of the addition process is 20-35°C.

Preferably, in step 3), the mixing method of the zirconium salt solution and the hydrolysis accelerator solution can also be: place the zirconium salt solution and the hydrolysis accelerator solution in storage tanks respectively, and after preheating to the reaction temperature, add React in a molecular mixing intensified reactor to obtain an acidic reaction solution with a final pH value of 0-7.

Preferably, in step 3), the reaction temperature is 0-65°C, more preferably, the reaction temperature is 10-50°C; most preferably, the reaction temperature is 20-35°C.

Preferably, in step 3), the molecular mixing enhanced reactor is characterized in that the characteristic time of molecular mixing in the reactor is less than or equal to the characteristic time of nucleation of the zirconia precursor, including but not limited to: hypergravity reactor, Rotating packed bed reactors, rotary reactors, stator-rotor reactors, microchannel reactors, static mixing reactors, etc.

Preferably, in step 3), the high gravity reactor is selected from rotating packed bed type high gravity rotary bed reactor, baffle type high gravity rotary bed reactor, spiral channel type high gravity rotary bed reactor, stator-rotor Type high gravity rotating bed reactor or rotating disk type high gravity rotating bed reactor; preferably, the rotating speed of the rotating bed rotor is 300-5000rpm; more preferably, the rotating speed of the rotating bed rotor is 600-2500rpm. The rotational speed of the rotating bed rotor is regulated by a frequency-adjustable speed changer.

Preferably, in step 3), the microchannel reactor is selected from a sleeve-type annular microchannel reactor, a Y-shaped microchannel reactor, and a T-shaped microchannel reactor.

Preferably, in step 3), the molar flow rate ratio of the zirconium salt solution passing into the rotating packed bed reactor to the hydrolysis accelerator solution is 1:0.2 to 2.5; more preferably, the zirconium salt passing into the rotating packed bed reactor The molar flow rate ratio of the solution to the hydrolysis accelerator solution is 1:0.5-1.5.

Preferably, in step 3), the linear velocity of the nozzle of the zirconium salt solution into the rotating packed bed reactor is 1 to 6 m/s, and the linear velocity of the nozzle of the hydrolysis accelerator solution into the rotating packed bed reactor is 0.5 m/s. ~4m/s.

Preferably, in step 3), the sleeve-type annular microchannel reactor is composed of an outer tube and an inner tube to form a sleeve, and an annular gap is left between the inner tube and the outer tube to form an annular microchannel, and the annular The radial spacing of the microchannels is 100 μm to 5 mm. The continuous phase inlet and outlet are provided on the outer tube, and the dispersed phase inlet is provided at one end of the inner tube, and the other end is closed, and the shape of the closed end is cone or bullet shape. The wall of the adjacent columnar inner tube is provided with micropores along the circumference of the wall. The diameter of the micropores ranges from 0.5 to 100 μm. The opening rate of the columnar inner tube wall is 3% to 60%. Phase export.

Preferably, in step 3), the volume flow ratio of the zirconium salt solution passing into the microchannel reactor and the hydrolysis accelerator solution is 1:0.2 to 1.0; more preferably, the zirconium salt solution passing into the microchannel reactor and the hydrolysis accelerator solution are The volume flow ratio of the accelerator solution is 1:0.4-0.8.

Preferably, in step 3), the flow rate of the zirconium salt solution into the outer tube of a single sleeve-type annular microchannel reactor is 1 to 4L/min, and the hydrolysis accelerator solution is passed into the inner tube of a single sleeve-type annular microchannel reactor The flow rate is 0.2~3L/min.

Preferably, in step 3), a plurality of microchannel reactors are used in parallel.

Preferably, in step 3), a centrifugal pump, a peristaltic pump or a metering pump with a flow meter is used to adjust the solution injection rate.

Preferably, in step 3), after the zirconium salt solution and the hydrolysis accelerator solution are reacted in a molecular mixing enhanced reactor to obtain an acidic reaction solution, the step of ultrasonically treating the acidic reaction solution is also included; preferably, the The ultrasonic treatment time is 0-120 min; more preferably, the ultrasonic treatment time is 15-40 min.

Preferably, in step 4), the aging treatment temperature is 10-80°C, and the aging treatment time is 0-8h.

More preferably, in step 4), the aging treatment temperature is 20-70°C, and the aging treatment time is 0.5-6h;

Most preferably, in step 4), the aging treatment time is 0.5-4 hours.

The purpose of the aging treatment is to make the precursor contained in the reaction solution more uniform, and it is also beneficial to improve the quality of the subsequent hydrothermal process.

Preferably, in step 4), the washing method is one or more of filtration (suction filtration or pressure filtration), dialysis, ultrafiltration, nanofiltration, and centrifugation;

More preferably, in step 4), the washing method is one or more of suction filtration, dialysis and ultrafiltration in combination.

Preferably, in step 4), the solvent in the precursor dispersion is one or more of water, ethanol, ethylene glycol, isopropanol, and ethyl acetate.

More preferably, in step 4), the solvent in the precursor dispersion is one or more of water, ethanol, and ethylene glycol.

Most preferably, in step 4), the solvent in the precursor dispersion liquid is one or both of water and ethylene glycol.

Preferably, in step 5), the hydrothermal reaction temperature is 130°C-250°C, and the hydrothermal reaction time is 1-48h;

More preferably, in step 5), the hydrothermal reaction temperature is 150°C-240°C, and the hydrothermal reaction time is 2-24h;

Most preferably, in step 5), the hydrothermal reaction temperature is 160°C-220°C, and the hydrothermal reaction time is 3-15h.

Preferably, in step 5), the hydrothermal medium in the product transparent nano-zirconia liquid phase dispersion can also be replaced by other liquid phase media to obtain transparent nano-zirconia dispersions of different liquid phase media; The phase medium is water, an organic solvent, a mixture of a water-miscible organic solvent and water or a mixture of different organic solvents; the organic solvent is selected from one or more of the following substances: methanol, ethanol, ethylene glycol, di Ethylene glycol, propylene glycol, glycerol, n-propanol, isopropanol, n-butanol, isobutanol, acetic acid, acetonitrile, N-N dimethylformamide, acetone, aniline, dimethylsulfoxide, tetrahydrofuran, pyridine, Ethyl acetate, methyl acetate, and butyl acetate. The organic solvent has relatively high polarity and low surface tension, which is beneficial to the stable dispersion of nano zirconia particles.

Preferably, in step 5), the method for replacing the hydrothermal medium with other liquid-phase medium can be any method generally known; but preferably, the method for replacing the hydrothermal medium with other liquid-phase medium It can be one or more of methods such as centrifugal displacement method, vacuum distillation displacement method, atmospheric pressure distillation displacement method, ultrafiltration displacement method, dialysis displacement method, solvent extraction method; more preferably, the hydrothermal medium is replaced by The method of other liquid medium can be one or more of centrifugal replacement method, vacuum distillation replacement method, atmospheric pressure distillation replacement method, and dialysis replacement method.

The present application found that by adjusting various reaction conditions such as reaction medium, hydrothermal medium, and pH, nano-zirconia particles can be charged with a certain amount of positive charges, thereby polarizing the molecules of the dispersion medium with a certain polarity and forming a double charge. The layer structure surrounds the surface of the particles, making it difficult for them to collide or agglomerate with each other, and then they can be stably dispersed in the water phase, different organic phases and their mixed phases, without introducing any auxiliary dispersing substances, avoiding The agglomeration between particles is successfully controlled in a very small range, so that the nano-zirconia particles form a stable monodispersion in the liquid phase, which effectively improves the transparency of the dispersion, thereby greatly broadening the scope of production. Its scope of use and application performance.

The process of preparing transparent nano-zirconia liquid phase dispersion includes a series of processes such as hydrolysis, aging, purification, hydrothermal and so on. It is extremely important to control the reaction speed, temperature and pH value. The positive charge of zirconia nanoparticles This is achieved by precisely controlling the conditions of the preparation process. If the hydrolysis speed is too fast, it will cause uneven particle size of the precursor and agglomeration between particles. The temperature and the pH value at the end of the reaction will affect the number of positive charges. If the number of charges is insufficient, the particles will agglomerate and the particle size will increase, which will affect the dispersion, transparency and stability of the dispersion, and then affect the performance of the product. . In addition, the temperature, time and purification process of hydrothermal and aging will also have a certain impact on the performance of the dispersion. Therefore, in order to obtain a transparent and stable nano-zirconia liquid phase dispersion, it is necessary to strictly control the above conditions.

The viscosity, solubility, and polarity of different solvents are different, so the hydrolysis speed and charge amount will be different. In addition, the affinity between different dispersion media and nano-zirconia particles is also slightly different, so the optimal preparation conditions will be slightly different. In addition to the difference in refractive index, there will be certain differences in the transparency and visible light transmittance of nano-zirconia liquid dispersions in different dispersion media.

In the present invention, how to keep the particle size of the zirconia nanoparticles after precipitation and decomposition of the precursor in such a small range of 1-12nm, and keep the nanoparticles from agglomerating during the whole process of hydrothermal decomposition, is the problem overcome by the present invention. First and foremost technical issues. In order to overcome the above-mentioned technical problems, the present invention achieves the purpose of controlling the amount of positive charge of the precursor by adjusting the reaction pH value, reaction medium, reaction temperature and other conditions, and adopts a hydrothermal medium with high electric double layer stability, and at the same time through the washing method The coordination of preparation conditions such as hydrothermal time, temperature, and rotational speed, after a series of precise and large-scale adjustments, ensured that the electrical double layer of the precursor would not be damaged during the entire hydrothermal process, and finally achieved no surface modification. The whole process of stable dispersion and no agglomeration under the condition of neutral agent makes the product have high purity, high crystallinity, good dispersion effect, no sedimentation after standing for ≥6 months, good thermal stability, and extreme conditions such as high temperature and high pressure will not affect the use. And the liquid phase dispersion can use water, organic solvent or their mixture as the dispersion medium, which provides great freedom and convenience for application. At the same time, the present invention shortens the time of hydrothermal treatment from at least one day in the prior art (patent 201180072212.5) to several hours, so that high-quality products can be obtained. Most importantly, the product obtained by the method of the present invention does not need any follow-up treatment, and the product after hydrothermal treatment is directly a good transparent nano-zirconia liquid phase dispersion, eliminating the need for washing, desalination, and sol after hydrothermal treatment. A large number of time-consuming and laborious post-treatment processes such as chemicalization and redissolution have laid a good foundation for the large-scale industrial preparation of zirconia liquid dispersions.

The third technical problem to be solved by the present invention is to provide an application of a transparent nano-zirconia liquid phase dispersion. The transparent nano-zirconia powder can be used as a special ceramic material due to its good dispersibility, such as dental ceramics, filters, piezoelectric elements, solid fuel cells, gas, temperature, sound, pressure, acceleration and humidity, etc. It can also be used to prepare catalysts and catalyst supports; zirconia has a strong affinity for organic phosphonic acid compounds and humic acids. Using this feature, transparent nano-zirconia liquid dispersions can be compounded with organic matter It is prepared as a separation membrane for the separation, extraction and purification of some alkylphosphonic acids, and can also be used for the treatment of sewage containing organic matter; high refractive index is one of the most important properties of zirconia, which makes the transparent nano-zirconia Dispersions can be used to manufacture optoelectronic components, optical waveguides, nonlinear optical materials, and optical sensors.

The beneficial effects of the present invention are as follows:

1) In the prior art, for the preparation of nano-zirconia and similar products that are easy to agglomerate, the effect of stable dispersion is often achieved by adding auxiliary substances such as surfactants. However, this practice not only introduces impurities into the product, but also complicates the preparation process and increases production costs due to the addition of auxiliary dispersing substances and the subsequent possible removal steps. The transparent nano-zirconia liquid phase dispersion of the present invention well overcomes the deficiencies in the prior art, and the prepared nano-zirconia liquid phase dispersion can achieve long-term stable and uniform dispersion without adding any surfactant in the preparation process Effect. The present invention overcomes the traditional hydrothermal method by controlling the positive charge of the precursor, adopting a hydrothermal medium with high electric double layer stability, and coordinating preparation conditions such as washing method, hydrothermal time, temperature, and rotational speed. Compared with other methods such as calcination, nano-oxides are easy to agglomerate. Compared with other methods such as calcination, they have the characteristics of low processing temperature, relatively difficult agglomeration, and narrow particle size distribution. In terms of preparing nanoparticles, compared with precipitation methods and other methods, the obtained particle size is small and uniform, and the crystallinity is high.

2) The nano zirconia dispersion particles prepared by the present invention are positively charged, and form an electric double layer structure in a dispersion medium with a certain polarity, making it difficult for them to collide or agglomerate with each other, relying on this electric double layer structure, The zirconia particles can form a stable monodispersion in the liquid phase without adding any auxiliary stabilizing surfactant.

3) The zirconia particles in the transparent nano-zirconia liquid phase dispersion of the present invention have a small particle size, uniform particle size distribution, and a one-dimensional size of 1-12 nm. The particle size is smaller than that of similar products in the past, so that the product of the present invention has better transparency.

4) The solid content of the transparent nano-zirconia liquid phase dispersion prepared by the present invention can be regulated by changing the reaction feed concentration, and can also be regulated by concentrated means such as rotary steaming; ) can keep transparent and stable, and the solid content of the product is 1wt%-50wt%.

5) The technological process used in the present invention is simple and easy to operate, the raw materials are cheap and easy to obtain, easy to store, the product has high purity and good quality, and the experiment has strong repeatability and is easy to scale up.

6) The transparent nano-zirconia liquid phase dispersion obtained in the present invention uses water or various organic solvents or mixtures thereof as the liquid phase medium, has wide dispersibility and compatibility, and has great selectivity and adaptability in application.

Description of drawings

The specific implementation manners of the present invention will be further described in detail below in conjunction with the accompanying drawings.

Fig. 1 shows the transmission electron micrograph of the product obtained in Example 3 of the present invention.

Fig. 2 shows the transmission electron micrograph of the product obtained in Example 5 of the present invention.

Fig. 3 shows the transparent dispersion photo of the product obtained in Example 6 of the present invention after standing for 6 months.

Fig. 4 shows the transmission electron micrograph of the product obtained in Example 7 of the present invention.

Fig. 5 shows the transparent dispersion photo of the product obtained in Example 8 of the present invention after standing for 6 months.

Fig. 6 shows the transparent dispersion photo of the product obtained in Example 9 of the present invention after standing for 6 months.

Fig. 7 shows a schematic diagram of the high-gravity rotating packed bed reactor used in Example 11 of the present invention.

Fig. 8 shows a schematic diagram of the sleeve-type annular microchannel reactor used in Example 12 of the present invention.

detailed description

In order to illustrate the present invention more clearly, the present invention will be further described below in conjunction with preferred embodiments and accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. Those skilled in the art should understand that the content specifically described below is illustrative rather than restrictive, and should not limit the protection scope of the present invention.

Example 1

A preparation method of a transparent nano-zirconia liquid phase dispersion, comprising the following steps:

1) 1.74g zirconyl nitrate dihydrate was dissolved in 70ml ethanol to obtain a zirconyl nitrate solution;

2) Dissolve 0.6g of sodium hydroxide in 60ml of ethanol to obtain a sodium hydroxide solution;

3) Add the zirconyl nitrate solution dropwise to the sodium hydroxide solution, control the reaction temperature to 15°C, and the stirring rate to 800r/min, adjust and control the final pH value of the reaction system to 7 with the sodium hydroxide solution;

4) After reaching the final pH requirement of the reaction system, aging at a constant temperature of 65°C for 2 hours;

5) washing and purifying the solution with water to obtain a filter cake;

6) The purified filter cake was ultrasonically dispersed in 7.2 g of water, transferred to an autoclave, and hydrothermally treated at 150° C. for 24 hours to obtain a transparent and stable zirconia/water phase dispersion.

The obtained nanometer zirconia/water phase dispersion is clear and transparent, the liquid phase medium is water, and the solid content is 10 wt%, no precipitation occurs after standing for 6 months, and the dispersion remains transparent and stable. It can be seen from the test that the one-dimensional size of the obtained zirconia/water phase dispersion particles is 3-12 nm.

Example 2

A preparation method of a transparent nano-zirconia liquid phase dispersion, comprising the following steps:

1) 2.8g zirconium nitrate pentahydrate was dissolved in 100ml methanol to prepare zirconium nitrate solution;

2) 1.68g of potassium hydroxide was dissolved in 120ml of methanol to obtain potassium hydroxide solution;

3) The zirconium nitrate solution was added dropwise to the potassium hydroxide solution, the reaction temperature was controlled to be 35° C., the stirring rate was 600 r/min, and the potassium hydroxide solution was used to adjust and control the final pH value of the reaction system to be 5;

4) After reaching the final pH requirement of the reaction system, heat up to 55°C and age for 4 hours;

5) washing and purifying the solution with water to obtain a filter cake;

6) The purified filter cake was ultrasonically dispersed in 15.2 g of water, transferred to an autoclave, and subjected to hydrothermal treatment at 220° C. for 3 hours to obtain a transparent and stable zirconia/water phase dispersion.

The obtained zirconia/water phase dispersion is clear and transparent, the liquid phase medium is water, and the solid content is 5 wt%, no precipitation occurs after standing for 6 months, and the dispersion remains transparent and stable. It can be seen from the test that the one-dimensional size of the obtained zirconia/water phase dispersion particles is 1-10 nm; under the condition of 1 cm optical path, the transmittance to light with a wavelength of 550 nm is 87%.

Example 3

A preparation method of a transparent nano-zirconia liquid phase dispersion, comprising the following steps:

1) 2.1g zirconium oxychloride octahydrate was dissolved in 70ml water to obtain zirconium oxychloride solution;

2) Dissolve 0.24g of sodium hydroxide in 50ml of water to obtain a sodium hydroxide solution;

3) Add the sodium hydroxide solution dropwise to the zirconium oxychloride solution, control the reaction temperature to 20°C, stir at a rate of 500r/min, adjust and control the final pH value of the reaction system to 2 with sodium hydroxide solution;

4) After reaching the final pH requirement of the reaction system, heat up to 70°C and age for 1 hour;

5) transfer the solution to the dialysis bag for washing and purification;

6) Transfer the purified reaction solution into an autoclave, hydrothermally treat it at 190° C. for 12 hours, and adjust the concentration by rotary steaming to obtain a transparent and stable zirconia/water phase dispersion.

The obtained zirconia/water phase dispersion is clear and transparent, the liquid phase medium is water, and the solid content is 35 wt%, no precipitation occurs after standing for 6 months, and the dispersion remains transparent and stable. It can be known from the test that the one-dimensional size of the obtained zirconia/water phase dispersion particles is 3-10 nm.

Fig. 1 is a transmission electron microscope photo of the product obtained in Example 3 of the present invention. It can be seen from the figure that the particle size of the dispersion particles is 3-10 nm, and the particles are uniformly dispersed.

Example 4

A preparation method of a transparent nano-zirconia liquid phase dispersion, comprising the following steps:

1) 34.8g zirconyl nitrate dihydrate was dissolved in 1400ml acetonitrile to obtain zirconyl nitrate solution;

2) Dissolve 10g of potassium hydroxide in 1200ml of acetonitrile to obtain potassium hydroxide solution;

3) Add the zirconyl nitrate solution dropwise to the potassium hydroxide solution, control the reaction temperature to 30°C, and the stirring rate to 400r/min, adjust and control the final pH value of the reaction system to 4 with the potassium hydroxide solution;

4) After reaching the final pH value requirement of the reaction system, aging at 50°C for 3h;

5) After filtering the solution, washing and purifying with water and ethanol to obtain a filter cake;

6) Ultrasonic dispersion of the purified filter cake in 72 g of ethanol, transferred to an autoclave, and hydrothermal treatment at 240° C. for 10 h to obtain a transparent and stable zirconia/ethanol phase dispersion.

The obtained zirconia/alcohol phase dispersion is clear and transparent, the liquid phase medium is ethanol, and the solid content is 20wt%, no precipitation occurs after standing for 6 months, and the dispersion remains transparent and stable. It can be seen from the test that the one-dimensional size of the obtained zirconia/water phase dispersion particles is 6-12 nm.

Example 5

A preparation method of a transparent nano-zirconia liquid phase dispersion, comprising the following steps:

1) 4.2g zirconium oxychloride octahydrate was dissolved in 130ml ethanol to obtain a zirconium oxychloride solution;

2) Dissolve 0.55g of sodium hydroxide in 130ml of ethanol to obtain a sodium hydroxide solution;

3) adding the sodium hydroxide solution dropwise to the zirconium oxychloride solution, controlling the reaction temperature to 25°C, stirring at a rate of 300r/min, adjusting and controlling the final pH value of the reaction system to 1 with ammonia solution;

4) After the final pH value requirement of the reaction system is reached, the temperature is raised to 65° C., and aged for 4 hours;

5) washing and purifying the solution with water to obtain a filter cake;

6) The purified filter cake was ultrasonically dispersed in 78.4 g of water, transferred to an autoclave, and hydrothermally treated at 210° C. for 5 hours to obtain a transparent and stable zirconia/water phase dispersion.

The obtained zirconia/water phase dispersion is clear and transparent, the liquid phase medium is water, and the solid content is 2 wt%, no precipitation occurs after standing for 6 months, and the dispersion remains transparent and stable. It can be seen from the test that the one-dimensional size of the obtained zirconia/water phase dispersion particles is 3-9 nm; under the condition of 1 cm optical path, the transmittance to light with a wavelength of 550 nm is 95%.

Fig. 2 is a transmission electron microscope photo of the product obtained in Example 5 of the present invention. It can be seen from the figure that the particle size of the dispersion particles is 3-9 nm, and the particles are uniformly dispersed.

Example 6

A preparation method of a transparent nano-zirconia liquid phase dispersion, comprising the following steps:

1) 10.45g zirconium oxychloride octahydrate was dissolved in 330ml water to obtain zirconium oxychloride solution;

2) Dissolving 4.55g of 25wt%-28wt% concentrated ammonia water in 330ml of water to prepare an ammonia solution;

3) adding the ammonia solution dropwise to the zirconium oxychloride solution, controlling the reaction temperature to 30°C, stirring at a rate of 900r/min, adjusting and controlling the final pH value of the reaction system to 3 with sodium hydroxide solution;

4) After reaching the final pH value requirement of the reaction system, raise the temperature to 80°C and age for 1.5h;

5) Transfer the solution to an ultrafiltration cup for washing and purification;

6) Transfer the purified reaction solution into an autoclave, hydrothermally treat it at 170° C. for 8 hours, and adjust the concentration by rotary steaming to obtain a transparent and stable zirconia/water phase dispersion.

The obtained zirconia/water phase dispersion is clear and transparent, the liquid phase medium is water, and the solid content is 20 wt%, no precipitation occurs after standing for 6 months, and the dispersion remains transparent and stable. It can be seen from the test that the one-dimensional size of the obtained zirconia/water phase dispersion particles is 4-10 nm.

Figure 3 is a photograph of the transparent dispersion of the product obtained in Example 6 of the present invention after standing for 6 months, as can be seen from the figure that the dispersion has good transparency and stability.

Example 7

A preparation method of a transparent nano-zirconia liquid phase dispersion, comprising the following steps:

1) 5.6g zirconium nitrate pentahydrate was dissolved in 140ml ethanol to obtain zirconium nitrate solution;

2) Dissolve 1.05g of sodium hydroxide in 125ml of ethanol to obtain a sodium hydroxide solution;

3) Add the sodium hydroxide solution dropwise to the zirconium nitrate solution, control the reaction temperature to 35° C., stir at a rate of 800 r/min, adjust and control the final pH value of the reaction system to 4.5 with sodium hydroxide solution;

4) After reaching the final pH requirement of the reaction system, heat up to 55°C and age for 3h;

5) washing and purifying the solution with water and ethylene glycol to obtain a filter cake;

6) The purified filter cake was ultrasonically dispersed in 38.4 g of ethylene glycol, transferred to an autoclave, and hydrothermally treated at 230° C. for 10 h to obtain a transparent and stable zirconia/ethylene glycol phase dispersion.

The obtained zirconia/ethylene glycol phase dispersion is clear and transparent, the liquid phase medium is ethylene glycol, and the solid content is 4 wt%, no precipitation occurs after standing for 6 months, and the dispersion remains transparent and stable. It can be seen from the test that the one-dimensional size of the obtained zirconia/water phase dispersion particles is 2-7 nm.

Fig. 4 is a transmission electron microscope photograph of the product obtained in Example 7 of the present invention after standing for 6 months. It can be seen from the figure that the particle size of the dispersion particles is 2-7 nm, and the particles are uniformly dispersed.

Example 8

A preparation method of a transparent nano-zirconia liquid phase dispersion, comprising the following steps:

1) 4.2g zirconium oxychloride octahydrate was dissolved in 65ml water to obtain zirconium oxychloride solution;

2) Dissolve 0.38g of sodium hydroxide in 40ml of water to obtain a sodium hydroxide solution;

3) Add the sodium hydroxide solution dropwise to the zirconium oxychloride solution, control the reaction temperature to 35°C, and stir at a rate of 500r/min, adjust and control the final pH value of the reaction system to 1.5 with sodium hydroxide solution;

4) After reaching the final pH requirement of the reaction system, raise the temperature to 65°C and age for 2 hours;

5) Transfer the solution to an ultrafiltration cup for washing and purification;

6) Transfer the purified reaction liquid into a high-pressure reactor, hydrothermally treat it at 200°C for 6 hours, and replace the medium with ethylene glycol by means of vacuum distillation replacement to obtain transparent and stable zirconia/ethylene glycol phase dispersion.

The obtained zirconia/ethylene glycol phase dispersion is clear and transparent, the liquid phase medium is ethylene glycol, and the solid content is 3 wt%, no precipitation occurs after standing for 6 months, and the dispersion remains transparent and stable. It can be known from the test that the one-dimensional size of the obtained zirconia/water phase dispersion particles is 3-10 nm.

Fig. 5 is a photograph of the transparent dispersion of the product obtained in Example 8 of the present invention after standing for 6 months. It can be seen from the figure that the dispersion has good transparency and stability.

Example 9

A preparation method of a transparent nano-zirconia liquid phase dispersion, comprising the following steps:

1) 4.2g zirconium oxychloride octahydrate was dissolved in 130ml ethanol to obtain a zirconium oxychloride solution;

2) Dissolve 0.55g of sodium hydroxide in 130ml of ethanol to obtain a sodium hydroxide solution;

3) Add the sodium hydroxide solution dropwise to the zirconium oxychloride solution, control the reaction temperature to 25° C., stir at a rate of 300 r/min, adjust and control the final pH value of the reaction system to 1 with sodium hydroxide solution;

4) After the final pH value requirement of the reaction system is reached, the temperature is raised to 45° C., and aged for 5 hours;

5) After the solution is centrifuged and purified with water, the supernatant is removed, and the solid substance in the lower layer is retained;

6) Ultrasonic disperse the purified precursor in 78.4g of water, transfer it to an autoclave, and conduct a hydrothermal treatment at 180°C for 24 hours, obtain a zirconia solid by centrifugation, and wash it repeatedly with N,N-dimethylformamide After ultrasonic dispersion in N,N-dimethylformamide.

The obtained zirconia/N,N-dimethylformamide phase dispersion is clear and transparent, the liquid phase medium is N,N-dimethylformamide, the solid content is 8wt%, no precipitation occurs after standing for 6 months, and the dispersion remains transparent and stable. It can be seen from the test that the one-dimensional size of the obtained zirconia/water phase dispersion particles is 3-10 nm; under the condition of 1 cm optical path, the transmittance to light with a wavelength of 550 nm is 79%.

Fig. 6 is a photo of the transparent dispersion of the product obtained in Example 9 of the present invention after standing for 6 months. It can be seen from the figure that the transparency and stability of the dispersion are good.

Example 10

A kind of application of transparent nanometer zirconia liquid phase dispersion, comprises the steps:

1) 5g polyvinylpyrrolidone film former is dissolved in 6ml water to make film former solution;

2) Measure 14 g of zirconia/aqueous phase transparent dispersion with a concentration of 8 wt%, add it to the above-mentioned film-forming agent solution, and ultrasonically disperse for 30 minutes to obtain a film-forming liquid;

3) Apply the film-forming solution evenly on the glass substrate by using a rotary glue coater, and dry it at 70° C. for 10 minutes to obtain a zirconia composite film product.

4) Take a blank film sample and a zirconia composite film sample, and measure their refractive index and transmittance.

The transmittance of the composite film can reach more than 95% of the blank sample in the visible and infrared light regions; the refractive index of the blank sample film is 1.52, while the refractive index of the zirconia composite film is 1.56. By changing the amount of zirconia added, it can be achieved Controllable refractive index of composite materials. Good transmittance and refractive index properties can make it used as optical waveguide, nonlinear optical material.

Example 11

The high gravity rotating packed bed reactor used in the present invention is prior art, such as disclosed patent (ZL95215430.7); The present invention adopts the high gravity rotating packed bed reactor schematic diagram as shown in Fig. The representative meanings are: 1-zirconium salt solution inlet, 2-hydrolysis accelerator solution inlet, 3-filler, 4-motor, 5-suspension outlet.

A method for preparing a transparent nano-zirconia liquid phase dispersion by utilizing a high-gravity rotating packed bed reactor, comprising the following steps:

1) Add 2000ml of an aqueous solution with a mass concentration of zirconium oxychloride octahydrate of 3.2% into the zirconium salt solution storage tank; add 2000ml of an aqueous solution with a mass concentration of sodium hydroxide of 0.5% into the hydrolysis accelerator solution storage tank;

2) Turn on the supergravity rotation device and adjust the rotation speed to 1200rpm;

3) Turn on the feed pump, transport the zirconium salt solution and the hydrolysis accelerator solution to the rotating bed at the same time for precipitation and crystallization reaction, and control the feed flow ratio of the zirconium salt solution and the hydrolysis accelerator solution to be 3:2 to control the reaction The temperature of the system is 25°C;

4) After the zirconium salt solution and the hydrolysis accelerator solution are fed, and the resulting reaction solution flows out of the supergravity rotating device, close the supergravity rotating device;

5) The resulting reaction solution is transferred to the dispersion tank, the ultrasonic dispersion device of the dispersion tank is opened, and the reaction solution is ultrasonically treated for 30 minutes;

6) The treated reaction solution flows into the high-pressure reactor after passing through the ultrafiltration purification device, and is heated at 170°C for 10 hours;

7) The hydrothermal product is placed in a rotary evaporator for concentration control to obtain a zirconia/water phase transparent dispersion.

The product is colorless and transparent, with a solid content of 13 wt%, and no sedimentation after standing for June. After testing, the one-dimensional size of the nano zirconia particles in the zirconia/water phase transparent dispersion is 2-8 nm.

Example 12

The sleeve-type annular microchannel reactor used in the present invention is a prior art, such as a published patent (200710177291.1 or 200810116581.X). The schematic diagram of the sleeve-type annular microchannel reactor adopted in the present invention is shown in FIG. 8 . The meanings represented by the numbers in the figure are: 6-inner tube, 7-outer tube, 8-continuous phase outlet, 9-annular microchannel, 10-microporous membrane, 11-continuous phase inlet, 12-dispersed phase fluid inlet , 13-flange.

A method for preparing a transparent nano-zirconia liquid phase dispersion by using a casing type annular microchannel reactor, comprising the following steps:

1) 2000ml of an aqueous solution with a mass concentration of zirconium oxychloride octahydrate of 6.4% is added in the zirconium salt solution storage tank; 2000ml of an aqueous solution with a mass concentration of sodium hydroxide of 1% is added in the storage tank of the hydrolysis accelerator solution;

2) Control the temperature of the reaction system to 25°C; turn on the feed pump, and simultaneously transport the zirconium salt solution and the hydrolysis accelerator solution to the sleeve-type annular microchannel reactor for precipitation and crystallization reaction, and control the zirconium salt solution and the hydrolysis accelerator solution The feed flow rates of the reagent solutions were 3L/min and 1.75L/min respectively;

3) The resulting reaction solution is transferred to the dispersion tank, the ultrasonic dispersion device of the dispersion tank is opened, and the reaction solution is ultrasonically treated for 30 minutes;

4) The treated reaction solution flows into the high-pressure reactor after passing through the ultrafiltration purification device, and is heated in water at 180°C for 10 hours;

5) The hydrothermal product is placed in a rotary evaporator for concentration control to obtain a zirconia/water phase transparent dispersion.

The product is colorless and transparent, with a solid content of 11wt%, and no sedimentation after standing for six months. After testing, the one-dimensional size of the nanometer zirconia particles in the zirconia/water phase transparent dispersion is 2-9 nm.

Example 13

Repeat Example 5, the only difference is that in step 1), 4.2g zirconium oxychloride octahydrate is dissolved in 130ml ethylene glycol, diethylene glycol, propylene glycol, glycerol, n-propanol, isopropanol One or more mixed liquids of alcohol, n-butanol, isobutanol, acetic acid, acetone, dimethyl sulfoxide, tetrahydrofuran, pyridine, ethyl acetate, methyl acetate, and butyl acetate to produce zirconium oxychloride Solution or zirconium oxychloride mixed solution; Its effect is similar to embodiment 5.

Example 14

Repeat Example 5, its difference is only, step 2) in, 0.55g sodium hydroxide is dissolved in 130ml ethylene glycol, diethylene glycol, propylene glycol, glycerol, n-propanol, Virahol, n-propanol One or more mixed liquids of butanol, isobutanol, acetic acid, acetone, dimethyl sulfoxide, tetrahydrofuran, pyridine, ethyl acetate, methyl acetate, and butyl acetate to prepare sodium hydroxide solution or hydroxide Sodium mixed solution; Its effect is similar to embodiment 5.

Example 15

Repeat Example 9, the only difference is that in step 6), the centrifuged product is ultrasonically dispersed in methanol, diethylene glycol, propylene glycol, glycerol, n-propanol, isopropanol, n-butanol, One or more mixed liquids of isobutanol, acetic acid, acetonitrile, acetone, aniline, dimethyl sulfoxide, tetrahydrofuran, pyridine, ethyl acetate, methyl acetate, and butyl acetate to prepare the corresponding transparent nano-zirconia liquid phase dispersion; its effect is similar to Example 9.

Example 16

Repeat Example 11, the only difference is that the molecular mixing intensified reactor used is a supergravity reactor, a rotary reactor, a stator-rotor reactor, a static mixing reactor, a Y-type microchannel reactor, a T-type microchannel reactor, and a T-type microchannel reactor. A kind of in channel reactor, all the other process conditions are similar; Its implementation effect is similar to embodiment 11.

Comparative example 1

Repeat Example 9, the only difference is that in step 6), the centrifugal product is ultrasonically dispersed in toluene or cyclohexane, and the product obtained is a white opaque suspension, which cannot exist stably. Obvious sedimentation and stratification will occur within 2 hours. It can be seen from this that the present invention needs to be dispersed in a solvent with a certain polarity, and the zirconia particles prepared in the present invention cannot achieve good dispersion in a non-polar solvent.

Comparative example 2

Repeat Example 3, the only difference is that in step 3), the pH value of the reaction solution is adjusted to the alkaline range, such as pH=8, 9, 10, 11, 12, 13, 14, the resulting particles produce Severe agglomeration, the product is an opaque white suspension, and part of the sedimentation phenomenon occurs during the standing process. It can be seen that the present invention needs to control the reaction pH value in the acidic range, and the product made in the alkaline range can hardly be dispersed.

Comparative example 3

Repeat Example 5, the only difference is that in step 3), the hydrolysis reaction temperature is adjusted to 75 ° C, the product obtained can be stably dispersed, but the color is whitish, and the transparency is obviously reduced. It can be seen that the present invention needs to control the reaction temperature within the preferred range, and the products obtained beyond the range will agglomerate to a certain extent, and its application performance will obviously decline.

Comparative example 4

Repeat Example 3, the only difference is that in step 6), the hydrothermal temperature is adjusted to 110° C., the resulting product has poor crystallinity and cannot completely convert from hydrated zirconia to zirconia. It can be seen that the present invention needs to control the hydrothermal temperature in the preferred range, and the products made beyond the range cannot meet the requirements.

Comparative example 5

Repeat Example 12, the only difference is that in step 2), the zirconium salt solution and the hydrolysis accelerator solution feed flow are adjusted to 0.4L/min and 0.15L/min respectively, and the resulting product can be stably dispersed, but the color Whitening, transparency decreased significantly. It can be seen that the present invention needs to control the feed flow rate within the preferred range, and the products produced beyond the range will agglomerate to a certain extent, and its application performance will obviously decline.

Apparently, the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those of ordinary skill in the art can also make It is impossible to exhaustively list all the implementation modes here, and any obvious changes or changes derived from the technical solutions of the present invention are still within the scope of protection of the present invention.

Claims (10)

1. a transparent nano zirconium oxide liquid dispersion, it is characterised in that: include liquid phase medium and nanometer Zirconia particles, described nano zircite granule is evenly dispersed in liquid phase medium；Described dispersion Solid content is 1wt%～50wt%；One-dimensional a size of the 1 of described nano zircite granule～12nm；Institute Stating liquid phase medium is water, organic solvent, organic solvent miscible with water and the mixture of water or the most organic The mixture of solvent.

A kind of transparent nano zirconium oxide liquid dispersion the most according to claim 1, it is characterised in that: One or more in following material of described organic solvent: methanol, ethanol, ethylene glycol, diethyl two Alcohol, propylene glycol, glycerol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, acetic acid, acetonitrile, N-N Dimethylformamide, acetone, aniline, dimethyl sulfoxide, oxolane, pyridine, ethyl acetate, acetic acid Methyl ester and butyl acetate.

3. one kind as arbitrary in claim 1 or 2 as described in the preparation of transparent nano zirconium oxide liquid dispersion Method, it is characterised in that comprise the steps:

1) water intaking, organic solvent, organic solvent miscible with water and the mixture of water or different organic solvents Mixture as solvent, be added thereto to zirconates, prepare zirconium salt solution；

2) water intaking, organic solvent, organic solvent miscible with water and the mixture of water or different organic solvents Mixture as solvent, be added thereto to hydrolytic accelerating agent, prepare hydrolytic accelerating agent solution；

3) zirconium salt solution and hydrolytic accelerating agent solution are mixed, obtain acid reaction liquid；

4) ripening above-mentioned acid reaction liquid, washs the acid reaction liquid after ripening, To presoma dispersion；

5) presoma dispersion is carried out hydrothermal treatment consists, obtain product transparent nano zirconium oxide liquid dispersion.

The preparation method of a kind of transparent nano zirconium oxide liquid dispersion the most according to claim 3, It is characterized in that: step 1) in, one or more in following material of described zirconates: zirconium nitrate, Zirconyl nitrate, zirconium oxychloride and zirconium chloride；The concentration of described zirconium salt solution is 1wt%～30wt%；Institute State one or more in the following material of organic solvent: methanol, ethanol, ethylene glycol, diethylene glycol, Propylene glycol, glycerol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, acetic acid, acetonitrile, acetone, Dimethyl sulfoxide, oxolane, pyridine, ethyl acetate, methyl acetate and butyl acetate；

Preferably, the concentration of described zirconium salt solution is 1wt%～15wt%；

It is highly preferred that the concentration of described zirconium salt solution is 1wt%～5wt%.

The preparation method of a kind of transparent nano zirconium oxide liquid dispersion the most according to claim 3, It is characterized in that: step 2) in, one or more in following material of described hydrolytic accelerating agent: hydrogen Potassium oxide, sodium hydroxide, ammonia, triethanolamine and ethylenediamine；The concentration of described hydrolytic accelerating agent is 0.1 Wt%～20wt%；One or more in the following material of described solvent: water, methanol, ethanol, Ethylene glycol, diethylene glycol, propylene glycol, glycerol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, Acetonitrile, N-N dimethylformamide, acetone, aniline, dimethyl sulfoxide, oxolane, pyridine, acetic acid Ethyl ester, methyl acetate and butyl acetate；

Preferably, the concentration of described hydrolytic accelerating agent is 0.1wt%～10wt%；

It is highly preferred that the concentration of described hydrolytic accelerating agent is 0.1wt%～5wt%.

The preparation method of a kind of transparent nano zirconium oxide liquid dispersion the most according to claim 3, It is characterized in that: step 3) in, the hybrid mode of zirconium salt solution and hydrolytic accelerating agent solution is: in stirring Under state, hydrolytic accelerating agent solution is at the uniform velocity added dropwise in zirconium salt solution, controls acid reaction liquid Final ph is 0～7, stir speed (S.S.) >=300r/min, and adition process temperature is 0～65 DEG C；

Preferably, the final ph controlling acid reaction liquid is 0.5～6, stir speed (S.S.) >=500r/min, Adition process temperature is 10～50 DEG C；

It is highly preferred that control acid reaction liquid final ph be 1～5, adition process temperature be 20～ 35℃。

The preparation method of a kind of transparent nano zirconium oxide liquid dispersion the most according to claim 3, It is characterized in that: step 3) in, the hybrid mode of zirconium salt solution and hydrolytic accelerating agent solution is: by zirconates Solution and hydrolytic accelerating agent solution are respectively placed in storage tank, after being preheating to reaction temperature, join molecule and mix Close in enhanced reactor and react, obtain the acid reaction liquid that final ph is 0～7；

Preferably, described reaction temperature is 0～65 DEG C, and described molecular mixing enhanced reactor is hypergravity Reactor, rotating packed-bed reactor, rotatable reactor, rotor-stator reactor, micro passage reaction or Static mixing reactor；

It is highly preferred that described reaction temperature is 10～50 DEG C；

Most preferably, described reaction temperature is 20～35 DEG C.

The preparation method of a kind of transparent nano zirconium oxide liquid dispersion the most according to claim 3, It is characterized in that: step 4) in, the temperature of ripening is 10～80 DEG C, and the time of ripening is 0～8h, the mode of washing be filtration, dialysis, ultrafiltration, nanofiltration, centrifugal in one or more and use, Solvent in described presoma dispersion liquid is in water, ethanol, ethylene glycol, isopropanol, ethyl acetate Plant or multiple；

Preferably, the temperature of ripening is 20～70 DEG C, and the time of ripening is 0.5～6h, The mode of washing is one or more in sucking filtration, dialysis, ultrafiltration use, in described presoma dispersion liquid Solvent be one or more in water, ethanol, ethylene glycol；

It is highly preferred that the time of ripening is 0.5～4h, the solvent in described presoma dispersion liquid is One or both in water, ethylene glycol.

The preparation method of a kind of transparent nano zirconium oxide liquid dispersion the most according to claim 3, It is characterized in that: step 5) in, hydrothermal temperature is 130 DEG C～250 DEG C, and the hydro-thermal reaction time is 1 ～48h；Solvent in product transparent nano zirconium oxide liquid dispersion also can be replaced into other liquid phases be situated between Matter, to obtain the transparent nano zirconia dispersion of different liquid phase medium；Other liquid phase mediums described be water, Organic solvent, organic solvent miscible with water and the mixture of water or the mixture of different organic solvents；Institute State one or more in the following material of organic solvent: methanol, ethanol, ethylene glycol, diethylene glycol, Propylene glycol, glycerol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, acetic acid, acetonitrile, N-N bis- Methylformamide, acetone, aniline, dimethyl sulfoxide, oxolane, pyridine, ethyl acetate, acetic acid first Ester and butyl acetate.

Preferably, hydrothermal temperature is 150 DEG C～240 DEG C, and the hydro-thermal reaction time is 2～24h；

It is highly preferred that hydrothermal temperature is 160 DEG C～220 DEG C, the hydro-thermal reaction time is 3～15h.

10. the transparent nano zirconium oxide liquid dispersion as described in as arbitrary in claim 1 or 2 is preparation spy Different ceramic material, catalyst and catalyst carrier, separation film, photoelectric cell, optical waveguide, non-linear Application in optical material and optical pickocff.