CN112079380A - Method for preparing titanium dioxide - Google Patents
Method for preparing titanium dioxide Download PDFInfo
- Publication number
- CN112079380A CN112079380A CN202010954882.0A CN202010954882A CN112079380A CN 112079380 A CN112079380 A CN 112079380A CN 202010954882 A CN202010954882 A CN 202010954882A CN 112079380 A CN112079380 A CN 112079380A
- Authority
- CN
- China
- Prior art keywords
- tetrabutyl titanate
- titanium dioxide
- mixture
- solution
- amino acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/38—Particle morphology extending in three dimensions cube-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention relates to the field of a preparation method of titanium dioxide, and aims to provide a method for preparing titanium dioxide, wherein the scheme is provided, and the method comprises the steps of preparing a tetrabutyl titanate alcohol solution and hydrolyzing tetrabutyl titanate, wherein the preparing of the tetrabutyl titanate alcohol solution comprises the steps of dissolving tetrabutyl titanate in an alcohol solvent and dispersing by using ultrasonic waves to obtain the tetrabutyl titanate alcohol solution; the hydrolysis of the tetrabutyl titanate is carried out in an ultrasonic environment. The method provided by the invention is easy to control the experimental process and industrial production, and can prepare titanium dioxide with different crystal forms and different morphologies by adjusting experimental parameters.
Description
Technical Field
The invention relates to the field of a preparation method of titanium dioxide, in particular to a method for preparing titanium dioxide.
Background
Titanium dioxide (TiO)2) The photocatalyst has the advantages of high photocatalytic activity, good stability, no toxicity to human bodies, low price and the like, so that the photocatalyst is unique in a plurality of semiconductor photocatalysts, and the application fields of the photocatalyst are spread in various aspects of degradation of organic wastewater, reduction of heavy metal ions, air purification, sterilization, antifogging and the like. Therefore, by controlling the synthesis conditions of the materials,the research on the preparation mechanisms of various titanium dioxide and the development of related advanced production processes, and the screening of preparation methods suitable for industrial amplification so as to obtain high-quality nano titanium dioxide with different properties is one of the most active fields in the current related interdisciplinary research, so that the invention provides a method for preparing titanium dioxide.
Disclosure of Invention
The invention aims to provide a method for preparing titanium dioxide.
In order to achieve the purpose, the invention adopts the following technical scheme:
preparing titanium dioxide, including preparing tetrabutyl titanate alcoholic solution and hydrolyzing tetrabutyl titanate, wherein the preparing of the tetrabutyl titanate alcoholic solution includes dissolving tetrabutyl titanate in an alcohol solvent, and dispersing by using ultrasonic waves to obtain the tetrabutyl titanate alcoholic solution;
the hydrolysis of the tetrabutyl titanate is carried out in an ultrasonic environment.
Further, the hydrolysis process of the tetrabutyl titanate comprises dropwise adding an amino acid aqueous solution into the tetrabutyl titanate alcoholic solution.
Furthermore, the dropping speed range of the amino acid aqueous solution is selected from V/(30 & min) -V/(7.5 & min), wherein V is the volume of the amino acid aqueous solution.
Further, the alcohol solvent comprises absolute ethyl alcohol, and the specific process for preparing the tetrabutyl titanate alcohol solution comprises dissolving tetrabutyl titanate in absolute ethyl alcohol and dispersing for 10-30 min by using ultrasonic waves to obtain the tetrabutyl titanate alcohol solution.
Further, the preparation of the amino acid aqueous solution comprises the step of dissolving the amino acid in deionized water to obtain the amino acid aqueous solution, wherein the volume ratio of the absolute ethyl alcohol to the deionized water is (1-2): (1-2).
Further, the method also comprises the step of drying a solid product generated by hydrolysis of tetrabutyl titanate to obtain titanium hydroxide, wherein the drying temperature range is 70-90 ℃, and the drying time range is 0.5-2 hours.
Further, calcining the titanium hydroxide, wherein the calcining time range of the titanium hydroxide is selected from 1h to 3h, and the calcining temperature range is selected from 500 ℃ to 900 ℃.
The invention has the beneficial effects that:
1. the method provided by the invention is easy to control the experimental process and is easy for industrial production;
2. titanium dioxide with different crystal forms and different shapes can be prepared by adjusting experimental parameters, namely alcohol-water ratio, amino acid type, dropping speed of amino acid aqueous solution and calcining temperature;
3. the method prepares the titanium dioxide in the ultrasonic environment, and can obtain the precursor with uniform nucleation in the early stage of preparing the titanium dioxide, which is obviously different from the general preparation process of the titanium dioxide.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of titanium dioxide according to the invention under different orthogonal conditions;
FIG. 2 is an SEM (scanning electron microscope) image of titanium dioxide No. 1 of the present invention;
FIG. 3 is an SEM image of titanium dioxide No. 2 according to the present invention;
FIG. 4 is an SEM image of titanium dioxide No. 3 according to the present invention;
FIG. 5 is an SEM image of titanium dioxide No. 4 of the present invention;
FIG. 6 is an SEM image of titanium dioxide No. 5 of the present invention;
FIG. 7 is an SEM image of titanium dioxide No. 6 according to the present invention;
FIG. 8 is an SEM image of titanium dioxide No. 7 of the present invention;
FIG. 9 is an SEM image of titanium dioxide No. 8 of the present invention;
FIG. 10 is an SEM photograph of titanium dioxide No. 9 according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Referring to fig. 1 to 10, a method for preparing titanium dioxide includes the following specific embodiments:
in some instances, the temperature of the ultrasound environment may be, but is not limited to, room temperature, and the amino acids may be, but is not limited to, including L-valine, L-arginine, and L-serine;
example 1
Step one, preparing an ethanol solution of tetrabutyl titanate: measuring 15mL of tetrabutyl titanate, dissolving in 20mL of absolute ethanol, and dispersing for 10min by using an ultrasonic cleaner to obtain a tetrabutyl titanate ethanol solution;
step two, preparing an amino acid aqueous solution: weighing 0.02g of L-valine, and completely dissolving the L-valine in 10mL of deionized water to obtain an amino acid aqueous solution of the L-valine, wherein the volume ratio of the absolute ethyl alcohol to the deionized water is 2: 1;
step three, dropwise adding the amino acid aqueous solution into the tetrabutyl titanate ethanol solution at the dropping speed of 2mL/min under the ultrasonic environment (the temperature is 30 ℃) to obtain a mixed solution;
step four, continuously placing the mixed solution in an ultrasonic cleaning machine for reaction for 2 hours, and obtaining a mixture after the reaction is finished;
step five, performing centrifugal separation on the mixture, pouring out supernatant of the mixture after the centrifugal separation is finished, adding a certain amount of absolute ethyl alcohol into the mixture from which the supernatant is poured out, stirring the mixture for 2-5 min by using a glass rod, then performing centrifugal separation on the mixture by using a centrifugal machine, pouring out absolute ethyl alcohol solution in the mixture after the centrifugation is finished, repeating the centrifugal cleaning for three times in this way, and finishing the centrifugal cleaning of the mixture by using the absolute ethyl alcohol;
then, adding a certain amount of deionized water into the mixture washed by the absolute ethyl alcohol, stirring for 2-5 min by using a glass rod, centrifugally separating the mixture by using a centrifugal machine, pouring out the deionized water solution in the mixture after centrifugation is finished, and centrifugally washing the mixture by using the deionized water to obtain a solid substance;
sixthly, drying the solid substance in an oven at 70 ℃ for 1h to obtain titanium hydroxide;
step seven, putting the titanium hydroxide into a muffle furnace for calcination, wherein the calcination temperature is 500 ℃, the calcination time is 2 hours, and obtaining titanium dioxide powder after calcination;
and step eight, finally, filling the titanium dioxide obtained after calcination into a sample bag for later use.
XRD (X-ray diffraction) detection was carried out on the obtained titanium dioxide powder, as shown in FIG. 1(a), and the result showed that the particle size of the titanium dioxide powder was 29.84nm, the crystal type was anatase type titanium dioxide, and SEM (scanning electron microscope) observation was carried out on the obtained titanium dioxide powder, and as shown in FIG. 2, the morphology of titanium dioxide was spherical.
Example 2
Step one, preparing an ethanol solution of tetrabutyl titanate: measuring 15mL of tetrabutyl titanate, dissolving in 20mL of absolute ethanol, and dispersing for 20min by using an ultrasonic cleaning machine to obtain a tetrabutyl titanate ethanol solution;
step two, preparing an amino acid aqueous solution: weighing 0.02g of L-arginine, and completely dissolving the L-arginine in 10mL of deionized water to obtain an amino acid aqueous solution of the L-arginine, wherein the volume ratio of absolute ethyl alcohol to the deionized water is 2: 1;
step three, dropwise adding the aqueous solution of the amino acid into the tetrabutyl titanate ethanol solution at the dropping speed of 1mL/min under the ultrasonic environment (the temperature is 30 ℃) to obtain a mixed solution;
step four, continuously placing the mixed solution in an ultrasonic cleaning machine for reaction for 2 hours, and obtaining a mixture after the reaction is finished;
step five, performing centrifugal separation on the mixture, pouring out supernatant of the mixture after the centrifugal separation is finished, adding a certain amount of absolute ethyl alcohol into the mixture from which the supernatant is poured out, stirring the mixture for 2-5 min by using a glass rod, then performing centrifugal separation on the mixture by using a centrifugal machine, pouring out absolute ethyl alcohol solution in the mixture after the centrifugation is finished, repeating the centrifugal cleaning for three times in this way, and finishing the centrifugal cleaning of the mixture by using the absolute ethyl alcohol;
then, adding a certain amount of deionized water into the mixture washed by the absolute ethyl alcohol, stirring for 2-5 min by using a glass rod, centrifugally separating the mixture by using a centrifugal machine, pouring out the deionized water solution in the mixture after centrifugation is finished, and centrifugally washing the mixture by using the deionized water to obtain a solid substance;
sixthly, drying the solid substance in an oven at 80 ℃ for 2h to obtain titanium hydroxide;
step seven, putting the titanium hydroxide into a muffle furnace for calcination, wherein the calcination temperature is 700 ℃, the calcination time is 2 hours, and obtaining titanium dioxide powder after calcination;
and step eight, finally, filling the titanium dioxide obtained after calcination into a sample bag for later use.
XRD detection of the obtained product was carried out, as shown in FIG. 1(b), and the result showed that the particle size of the titanium dioxide powder was 44.95nm, the crystal type was rutile type, and SEM (scanning electron microscope) observation of the obtained titanium dioxide powder showed that the morphology of titanium dioxide was spherical and cubic, as shown in FIG. 3, and was a mixed structure.
Example 3
Step one, preparing an ethanol solution of tetrabutyl titanate: measuring 15mL of tetrabutyl titanate, dissolving in 20mL of absolute ethanol, and dispersing for 30min by using an ultrasonic cleaning machine to obtain a tetrabutyl titanate ethanol solution;
step two, preparing an amino acid aqueous solution: weighing 0.02g of L-serine, and completely dissolving the L-serine in 10mL of deionized water to obtain an amino acid aqueous solution of the L-serine, wherein the volume ratio of absolute ethyl alcohol to the deionized water is 2: 1;
step three, dropwise adding the amino acid aqueous solution into the tetrabutyl titanate ethanol solution at the dropping speed of 0.5mL/min under the ultrasonic environment (the temperature is 30 ℃) to obtain a mixed solution;
step four, continuously placing the mixed solution in an ultrasonic cleaning machine for reaction for 2 hours, and obtaining a mixture after the reaction is finished;
step five, performing centrifugal separation on the mixture, pouring out supernatant of the mixture after the centrifugal separation is finished, adding a certain amount of absolute ethyl alcohol into the mixture from which the supernatant is poured out, stirring the mixture for 2-5 min by using a glass rod, then performing centrifugal separation on the mixture by using a centrifugal machine, pouring out absolute ethyl alcohol solution in the mixture after the centrifugation is finished, repeating the centrifugal cleaning for three times in this way, and finishing the centrifugal cleaning of the mixture by using the absolute ethyl alcohol;
then, adding a certain amount of deionized water into the mixture washed by the absolute ethyl alcohol, stirring for 2-5 min by using a glass rod, centrifugally separating the mixture by using a centrifugal machine, pouring out the deionized water solution in the mixture after centrifugation is finished, and centrifugally washing the mixture by using the deionized water to obtain a solid substance;
sixthly, drying the solid substance in an oven at 90 ℃ for 1h to obtain titanium hydroxide;
step seven, putting the titanium hydroxide into a muffle furnace for calcination, wherein the calcination temperature is 900 ℃, the calcination time is 2 hours, and obtaining titanium dioxide powder after calcination;
and step eight, finally, filling the titanium dioxide obtained after calcination into a sample bag for later use.
XRD detection of the obtained product was carried out, as shown in FIG. 1(c), and the result showed that the particle size of the titanium dioxide powder was 42.74nm, the crystal type was rutile type, and SEM (scanning electron microscope) observation of the obtained titanium dioxide powder showed that the morphology of titanium dioxide was cubic as shown in FIG. 4.
Example 4
Step one, preparing an ethanol solution of tetrabutyl titanate: measuring 15mL of tetrabutyl titanate, dissolving in 15mL of absolute ethanol, and dispersing for 10min by using an ultrasonic cleaning machine to obtain a tetrabutyl titanate ethanol solution;
step two, preparing an amino acid aqueous solution: weighing 0.02g of L-valine, and completely dissolving the L-valine in 15mL of deionized water to obtain an amino acid aqueous solution of the L-serine, wherein the volume ratio of the absolute ethyl alcohol to the deionized water is 1: 1;
step three, dropwise adding the aqueous solution of the amino acid into the tetrabutyl titanate ethanol solution at the dropping speed of 1mL/min under the ultrasonic environment (the temperature is 30 ℃) to obtain a mixed solution;
step four, continuously placing the mixed solution in an ultrasonic cleaning machine for reaction for 2 hours, and obtaining a mixture after the reaction is finished;
step five, performing centrifugal separation on the mixture, pouring out supernatant of the mixture after the centrifugal separation is finished, adding a certain amount of absolute ethyl alcohol into the mixture from which the supernatant is poured out, stirring the mixture for 2-5 min by using a glass rod, then performing centrifugal separation on the mixture by using a centrifugal machine, pouring out absolute ethyl alcohol solution in the mixture after the centrifugation is finished, repeating the centrifugal cleaning for three times in this way, and finishing the centrifugal cleaning of the mixture by using the absolute ethyl alcohol;
then, adding a certain amount of deionized water into the mixture washed by the absolute ethyl alcohol, stirring for 2-5 min by using a glass rod, centrifugally separating the mixture by using a centrifugal machine, pouring out the deionized water solution in the mixture after centrifugation is finished, and centrifugally washing the mixture by using the deionized water to obtain a solid substance;
sixthly, drying the solid substance in an oven at 70 ℃ for 0.5h to obtain titanium hydroxide;
step seven, putting the titanium hydroxide into a muffle furnace for calcination, wherein the calcination temperature is 900 ℃, the calcination time is 2 hours, and obtaining titanium dioxide powder after calcination;
and step eight, finally, filling the titanium dioxide obtained after calcination into a sample bag for later use.
XRD analysis of the obtained product showed that the particle size of the titanium dioxide powder was 44.13nm and the crystal type was rutile as shown in FIG. 1(d), and SEM (scanning Electron microscope) observation of the obtained titanium dioxide powder showed that the morphology of titanium dioxide was cubic as shown in FIG. 5.
Example 5
Step one, preparing an ethanol solution of tetrabutyl titanate: measuring 15mL of tetrabutyl titanate, dissolving in 15mL of absolute ethanol, and dispersing for 30min by using an ultrasonic cleaning machine to obtain a tetrabutyl titanate ethanol solution;
step two, preparing an amino acid aqueous solution: weighing 0.02g of L-arginine, and completely dissolving the L-arginine in 15mL of deionized water to obtain an amino acid aqueous solution of the L-arginine, wherein the volume ratio of absolute ethyl alcohol to the deionized water is 1: 1;
step three, dropwise adding the amino acid aqueous solution into the tetrabutyl titanate ethanol solution at the dropping speed of 0.5mL/min under the ultrasonic environment (the temperature is 30 ℃) to obtain a mixed solution;
step four, continuously placing the mixed solution in an ultrasonic cleaning machine for reaction for 2 hours, and obtaining a mixture after the reaction is finished;
step five, performing centrifugal separation on the mixture, pouring out supernatant of the mixture after the centrifugal separation is finished, adding a certain amount of absolute ethyl alcohol into the mixture from which the supernatant is poured out, stirring the mixture for 2-5 min by using a glass rod, then performing centrifugal separation on the mixture by using a centrifugal machine, pouring out absolute ethyl alcohol solution in the mixture after the centrifugation is finished, repeating the centrifugal cleaning for three times in this way, and finishing the centrifugal cleaning of the mixture by using the absolute ethyl alcohol;
then, adding a certain amount of deionized water into the mixture washed by the absolute ethyl alcohol, stirring for 2-5 min by using a glass rod, centrifugally separating the mixture by using a centrifugal machine, pouring out the deionized water solution in the mixture after centrifugation is finished, and centrifugally washing the mixture by using the deionized water to obtain a solid substance;
sixthly, drying the solid substance in an oven at 80 ℃ for 2h to obtain titanium hydroxide;
step seven, putting the titanium hydroxide into a muffle furnace for calcination, wherein the calcination temperature is 500 ℃, the calcination time is 2 hours, and obtaining titanium dioxide powder after calcination;
and step eight, finally, filling the titanium dioxide obtained after calcination into a sample bag for later use.
XRD detection of the obtained product was carried out, as shown in FIG. 1(e), and the result showed that the particle diameter of the titanium dioxide powder was 22.48nm and the crystal type was anatase, and SEM (scanning electron microscope) observation of the obtained titanium dioxide powder showed that the morphology of titanium dioxide was spherical as shown in FIG. 6.
Example 6
Step one, preparing an ethanol solution of tetrabutyl titanate: measuring 15mL of tetrabutyl titanate, dissolving in 15mL of absolute ethanol, and dispersing for 30min by using an ultrasonic cleaning machine to obtain a tetrabutyl titanate ethanol solution;
step two, preparing an amino acid aqueous solution: weighing 0.02g of L-serine, and completely dissolving the L-serine in 15mL of deionized water to obtain an amino acid aqueous solution of the L-serine, wherein the volume ratio of absolute ethyl alcohol to the deionized water is 1: 1;
step three, dropwise adding the amino acid aqueous solution into the tetrabutyl titanate ethanol solution at the dropping speed of 2mL/min under the ultrasonic environment (the temperature is 30 ℃) to obtain a mixed solution;
step four, continuously placing the mixed solution in an ultrasonic cleaning machine for reaction for 2 hours, and obtaining a mixture after the reaction is finished;
step five, performing centrifugal separation on the mixture, pouring out supernatant of the mixture after the centrifugal separation is finished, adding a certain amount of absolute ethyl alcohol into the mixture from which the supernatant is poured out, stirring the mixture for 2-5 min by using a glass rod, then performing centrifugal separation on the mixture by using a centrifugal machine, pouring out absolute ethyl alcohol solution in the mixture after the centrifugation is finished, repeating the centrifugal cleaning for three times in this way, and finishing the centrifugal cleaning of the mixture by using the absolute ethyl alcohol;
then, adding a certain amount of deionized water into the mixture washed by the absolute ethyl alcohol, stirring for 2-5 min by using a glass rod, centrifugally separating the mixture by using a centrifugal machine, pouring out the deionized water solution in the mixture after centrifugation is finished, and centrifugally washing the mixture by using the deionized water to obtain a solid substance;
sixthly, drying the solid substance in an oven at 80 ℃ for 2h to obtain titanium hydroxide;
step seven, putting the titanium hydroxide into a muffle furnace for calcination, wherein the calcination temperature is 700 ℃, the calcination time is 2 hours, and obtaining titanium dioxide powder after calcination;
and step eight, finally, filling the titanium dioxide obtained after calcination into a sample bag for later use.
XRD detection of the obtained product was carried out, as shown in FIG. 1(f), and as a result, it was revealed that the particle diameter of the titanium dioxide powder was 35.82nm and the crystal type was rutile type, and as shown in FIG. 7, the morphology of the titanium dioxide powder was spherical and cubic as observed by SEM (scanning electron microscope).
Example 7
Step one, preparing an ethanol solution of tetrabutyl titanate: measuring 15mL of tetrabutyl titanate, dissolving in 10mL of absolute ethanol, and dispersing for 30min by using an ultrasonic cleaning machine to obtain a tetrabutyl titanate ethanol solution;
step two, preparing an amino acid aqueous solution: weighing 0.02g of L-valine, and completely dissolving the L-valine in 20mL of deionized water to obtain an amino acid aqueous solution of the L-valine, wherein the volume ratio of the absolute ethyl alcohol to the deionized water is 1: 2;
step three, dropwise adding the amino acid aqueous solution into the tetrabutyl titanate ethanol solution at the dropping speed of 0.5mL/min under the ultrasonic environment (the temperature is 30 ℃) to obtain a mixed solution;
step four, continuously placing the mixed solution in an ultrasonic cleaning machine for reaction for 2 hours, and obtaining a mixture after the reaction is finished;
step five, performing centrifugal separation on the mixture, pouring out supernatant of the mixture after the centrifugal separation is finished, adding a certain amount of absolute ethyl alcohol into the mixture from which the supernatant is poured out, stirring the mixture for 2-5 min by using a glass rod, then performing centrifugal separation on the mixture by using a centrifugal machine, pouring out absolute ethyl alcohol solution in the mixture after the centrifugation is finished, repeating the centrifugal cleaning for three times in this way, and finishing the centrifugal cleaning of the mixture by using the absolute ethyl alcohol;
then, adding a certain amount of deionized water into the mixture washed by the absolute ethyl alcohol, stirring for 2-5 min by using a glass rod, centrifugally separating the mixture by using a centrifugal machine, pouring out the deionized water solution in the mixture after centrifugation is finished, and centrifugally washing the mixture by using the deionized water to obtain a solid substance;
sixthly, drying the solid substance in an oven at 80 ℃ for 2h to obtain titanium hydroxide;
step seven, putting the titanium hydroxide into a muffle furnace for calcination, wherein the calcination temperature is 700 ℃, the calcination time is 2 hours, and obtaining titanium dioxide powder after calcination;
and step eight, finally, filling the titanium dioxide obtained after calcination into a sample bag for later use.
XRD detection of the obtained product was carried out, as shown in FIG. 1(g), and as a result, it was revealed that the particle diameter of the titanium dioxide powder was 38.55nm and the crystal type was rutile type, and as shown in FIG. 8, the morphology of the titanium dioxide powder was spherical and cubic as observed by SEM (scanning electron microscope).
Example 8
Step one, preparing an ethanol solution of tetrabutyl titanate: measuring 15mL of tetrabutyl titanate, dissolving in 10mL of absolute ethanol, and dispersing for 30min by using an ultrasonic cleaning machine to obtain a tetrabutyl titanate ethanol solution;
step two, preparing an amino acid aqueous solution: weighing 0.02g of L-arginine, and completely dissolving the L-arginine in 20mL of deionized water to obtain an amino acid aqueous solution of the L-arginine, wherein the volume ratio of absolute ethyl alcohol to the deionized water is 1: 2;
step three, dropwise adding the amino acid aqueous solution into the tetrabutyl titanate ethanol solution at the dropping speed of 2mL/min under the ultrasonic environment (the temperature is 30 ℃) to obtain a mixed solution;
step four, continuously placing the mixed solution in an ultrasonic cleaning machine for reaction for 2 hours, and obtaining a mixture after the reaction is finished;
step five, performing centrifugal separation on the mixture, pouring out supernatant of the mixture after the centrifugal separation is finished, adding a certain amount of absolute ethyl alcohol into the mixture from which the supernatant is poured out, stirring the mixture for 2-5 min by using a glass rod, then performing centrifugal separation on the mixture by using a centrifugal machine, pouring out absolute ethyl alcohol solution in the mixture after the centrifugation is finished, repeating the centrifugal cleaning for three times in this way, and finishing the centrifugal cleaning of the mixture by using the absolute ethyl alcohol;
then, adding a certain amount of deionized water into the mixture washed by the absolute ethyl alcohol, stirring for 2-5 min by using a glass rod, centrifugally separating the mixture by using a centrifugal machine, pouring out the deionized water solution in the mixture after centrifugation is finished, and centrifugally washing the mixture by using the deionized water to obtain a solid substance;
sixthly, drying the solid substance in an oven at 80 ℃ for 2h to obtain titanium hydroxide;
step seven, putting the titanium hydroxide into a muffle furnace for calcination, wherein the calcination temperature is 900 ℃, the calcination time is 2 hours, and obtaining titanium dioxide powder after calcination;
and step eight, finally, filling the titanium dioxide obtained after calcination into a sample bag for later use.
XRD detection of the obtained product was carried out, as shown in FIG. 1(h), and the result showed that the particle size of the titanium dioxide powder was 41.86nm, the crystal type was rutile type, and SEM (scanning electron microscope) observation of the obtained titanium dioxide powder showed that the morphology of titanium dioxide was cubic as shown in FIG. 9.
Example 9
Step one, preparing an ethanol solution of tetrabutyl titanate: measuring 15mL of tetrabutyl titanate, dissolving in 10mL of absolute ethanol, and dispersing for 30min by using an ultrasonic cleaning machine to obtain a tetrabutyl titanate ethanol solution;
step two, preparing an amino acid aqueous solution: weighing 0.02g of L-serine, and completely dissolving the L-serine in 20mL of deionized water to obtain an amino acid aqueous solution of the L-serine, wherein the volume ratio of absolute ethyl alcohol to the deionized water is 1: 2;
step three, dropwise adding the aqueous solution of the amino acid into the tetrabutyl titanate ethanol solution at the dropping speed of 1mL/min under the ultrasonic environment (the temperature is 30 ℃) to obtain a mixed solution;
step four, continuously placing the mixed solution in an ultrasonic cleaning machine for reaction for 2 hours, and obtaining a mixture after the reaction is finished;
step five, performing centrifugal separation on the mixture, pouring out supernatant of the mixture after the centrifugal separation is finished, adding a certain amount of absolute ethyl alcohol into the mixture from which the supernatant is poured out, stirring the mixture for 2-5 min by using a glass rod, then performing centrifugal separation on the mixture by using a centrifugal machine, pouring out absolute ethyl alcohol solution in the mixture after the centrifugation is finished, repeating the centrifugal cleaning for three times in this way, and finishing the centrifugal cleaning of the mixture by using the absolute ethyl alcohol;
then, adding a certain amount of deionized water into the mixture washed by the absolute ethyl alcohol, stirring for 2-5 min by using a glass rod, centrifugally separating the mixture by using a centrifugal machine, pouring out the deionized water solution in the mixture after centrifugation is finished, and centrifugally washing the mixture by using the deionized water to obtain a solid substance;
sixthly, drying the solid substance in an oven at 80 ℃ for 2h to obtain titanium hydroxide;
step seven, putting the titanium hydroxide into a muffle furnace for calcination, wherein the calcination temperature is 500 ℃, the calcination time is 2 hours, and obtaining titanium dioxide powder after calcination;
and step eight, finally, filling the titanium dioxide obtained after calcination into a sample bag for later use.
XRD detection of the obtained product was carried out, as shown in FIG. 1(i), and as a result, it was revealed that the particle diameter of the titanium dioxide powder was 22.37nm, the crystal type was anatase, and SEM (scanning electron microscope) observation of the obtained titanium dioxide powder showed spherical and cubic shapes as shown in FIG. 10.
The XRD patterns of titanium dioxide samples from No. 1 to No. 9 are respectively shown in the (a) - (i) of the titanium dioxide samples from No. 1 to No. 9 in sequence, and the results of the above examples show that the particle size of the titanium dioxide is constantly changed, the minimum particle size is 22.37nm, the maximum particle size is 44.95nm, and the titanium dioxide is all nano-scale in size, which indicates that the nano-scale titanium dioxide is prepared by the method;
the results show that under the ultrasonic environment, by changing four factors (alcohol-water ratio, amino acid type, dropping speed of amino acid aqueous solution and calcining temperature) in the orthogonal table, the crystal form of the titanium dioxide is changed in such a way that the titanium dioxide obtained by the samples No. 1, No. 5 and No. 9 belongs to anatase type titanium dioxide, the titanium dioxide obtained by the samples No. 1, No. 5 and No. 9 belongs to rutile type titanium dioxide except the samples No. 1, No. 5 and No. 9, the obtained titanium dioxide belongs to anatase type when the calcining temperature is 500 ℃ (No. 1, No. 5 and No. 9), and the obtained titanium dioxide belongs to rutile type when the calcining temperature is more than 500 ℃ and less than or equal to 900;
when orthogonal data are analyzed by a pole difference method, as shown in the following table 2, four factors (alcohol-water ratio, amino acid type, dropping speed of amino acid aqueous solution and calcining temperature) have influence on the particle size of the nano titanium dioxide, and the influence degrees are in turn from large to small: the calcination temperature is greater than the alcohol-water ratio and the amino acid type is greater than the dripping speed of the amino acid water solution, so that the influence of the calcination temperature on the particle size of the titanium dioxide is large, and the titanium dioxide with the required particle size can be obtained by controlling the calcination temperature;
performing SEM observation on the obtained titanium dioxide powder, as shown in FIG. 2, which shows that the titanium dioxide is spherical, SEM images of the titanium dioxide under different orthogonal conditions are shown in FIGS. 2-10, which sequentially represent No. 1-9 samples in Table 1, and it can be found that the shapes of the No. 1, No. 5 and No. 9 samples are spherical, the shapes of the No. 2, No. 6 and No. 7 samples are mixture of spherical and cubic, and the shapes of the No. 3, No. 4 and No. 8 samples are cubic, so that the calcination temperature has a large influence on the shape of the titanium dioxide, and the titanium dioxide with the required shape can be obtained by controlling the calcination temperature;
the calcination temperature and other three factors (alcohol-water ratio, amino acid type and dropping speed of amino acid aqueous solution) are easy to control, so that the purposes of easy control of the experimental process and easy industrial production are achieved;
therefore, under the ultrasonic environment, the calcining temperature is increased, other three factors (alcohol-water ratio, amino acid type and the dropping speed of amino acid aqueous solution) are changed, the shape of the titanium dioxide is firstly transited from the sphere to the mixture of the sphere and the cube, and finally the titanium dioxide is changed into the cube structure, comprehensively, the calcining temperature not only influences the particle size and the crystal type of the titanium dioxide, but also influences the micro shape, and the required titanium dioxide with the corresponding crystal form and shape can be obtained by changing the corresponding experimental conditions according to the actual requirements, so that the aim of preparing the titanium dioxide with different crystal forms and different shapes by adjusting the experimental parameters, namely the alcohol-water ratio, the amino acid type, the dropping speed of the amino acid aqueous solution and the calcining temperature is fulfilled;
the principle of ultrasound can be explained by the phenomenon of "cavitation", wherein the power density of the ultrasonic vibration is 0.35w/cm when the pressure of the sound wave transmitted in the liquid reaches one atmosphere2At this time, the sound wave pressure peak of the ultrasonic wave can reach vacuum or negative pressure, but actually no negative pressure exists, so that the ultrasonic wave is produced in the liquidGenerates a large force to pull and crack liquid molecules into hollow holes and cavitation cores. The cavity is very close to a vacuum and collapses when the ultrasonic pressure reverses to a maximum, and the solid material is sufficiently dispersed by the intense impact of the collapse, a phenomenon known as "cavitation" in which numerous tiny cavitation bubbles collapse. The ultrasonic cavitation energy is utilized to accelerate and control the chemical reaction, so that the nucleation and the growth of the chemical reaction are uniform, and fine particles are expected to be obtained.
The invention accelerates and controls the preparation of tetrabutyl titanate alcoholic solution and the hydrolysis of tetrabutyl titanate in the preparation process of titanium dioxide by utilizing ultrasonic cavitation energy, so that the nucleation and the growth of titanium hydroxide are relatively uniform, a precursor with uniform nucleation is obtained at the early stage of preparing the titanium dioxide, and fine titanium dioxide particles can be obtained in the later preparation process.
Table 1 shows the parameters of the orthogonal experiment
TABLE 1
Table 2 is a data result analysis table of orthogonal experiment calculated by a range difference method
TABLE 2
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. A method for preparing titanium dioxide, comprising the preparation of an alcoholic solution of tetrabutyl titanate and the hydrolysis of tetrabutyl titanate,
the preparation of the tetrabutyl titanate alcoholic solution comprises the steps of dissolving tetrabutyl titanate in an alcohol solvent, and dispersing by using ultrasonic waves to obtain the tetrabutyl titanate alcoholic solution;
the hydrolysis of the tetrabutyl titanate is carried out in an ultrasonic environment.
2. The method of claim 1, wherein the hydrolysis of tetrabutyl titanate comprises adding an aqueous amino acid solution dropwise to an alcoholic tetrabutyl titanate solution.
3. The method for producing titanium dioxide according to claim 2, wherein the dropping rate of the aqueous amino acid solution is selected from the range of V/(30-min) to V/(7.5-min), where V is the volume of the aqueous amino acid solution.
4. The method for preparing titanium dioxide according to claim 3, wherein the alcohol solvent comprises absolute ethyl alcohol, and the specific process for preparing the tetrabutyl titanate alcohol solution comprises dissolving tetrabutyl titanate in absolute ethyl alcohol and dispersing for 10-30 min by using ultrasound to obtain a tetrabutyl titanate alcohol solution.
5. The method of claim 4, wherein the preparing of the amino acid aqueous solution comprises dissolving the amino acid in deionized water to obtain the amino acid aqueous solution, and the volume ratio of the absolute ethanol to the deionized water is (1-2): 1-2.
6. The method for preparing titanium dioxide according to claim 5, wherein the method comprises drying the solid product generated by hydrolysis of tetrabutyl titanate to obtain titanium hydroxide, wherein the drying temperature is selected from 70 ℃ to 90 ℃, and the drying time is selected from 0.5h to 2 h.
7. The method for preparing titanium dioxide according to claim 6, wherein the titanium hydroxide is calcined, the calcination time of the titanium hydroxide is selected to be 1-3 h, and the calcination temperature is selected to be 500-900 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010954882.0A CN112079380A (en) | 2020-09-11 | 2020-09-11 | Method for preparing titanium dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010954882.0A CN112079380A (en) | 2020-09-11 | 2020-09-11 | Method for preparing titanium dioxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112079380A true CN112079380A (en) | 2020-12-15 |
Family
ID=73737571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010954882.0A Pending CN112079380A (en) | 2020-09-11 | 2020-09-11 | Method for preparing titanium dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112079380A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112591792A (en) * | 2020-12-30 | 2021-04-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Simple preparation method of colored titanium dioxide for photocatalysis |
| CN112604688A (en) * | 2020-12-30 | 2021-04-06 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of ferroferric oxide loaded colored titanium dioxide for photocatalysis |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10114521A (en) * | 1996-10-07 | 1998-05-06 | Agency Of Ind Science & Technol | Superfine noble metal particle dispersed thin titanium dioxide film and its production |
| CN101486948A (en) * | 2008-12-31 | 2009-07-22 | 中国科学院宁波材料技术与工程研究所 | Titanium dioxide electrorheological liquid having heavy electrorheological effect under low field |
| CN103030176A (en) * | 2012-12-08 | 2013-04-10 | 安徽工程大学 | Synthesizing method for controlling change of morphology and crystal form of nanoscale titanium dioxide |
| CN111530485A (en) * | 2019-11-25 | 2020-08-14 | 中国石油大学(华东) | Carbon and nitrogen co-doped titanium dioxide nano material and preparation method and application thereof |
-
2020
- 2020-09-11 CN CN202010954882.0A patent/CN112079380A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10114521A (en) * | 1996-10-07 | 1998-05-06 | Agency Of Ind Science & Technol | Superfine noble metal particle dispersed thin titanium dioxide film and its production |
| CN101486948A (en) * | 2008-12-31 | 2009-07-22 | 中国科学院宁波材料技术与工程研究所 | Titanium dioxide electrorheological liquid having heavy electrorheological effect under low field |
| CN103030176A (en) * | 2012-12-08 | 2013-04-10 | 安徽工程大学 | Synthesizing method for controlling change of morphology and crystal form of nanoscale titanium dioxide |
| CN111530485A (en) * | 2019-11-25 | 2020-08-14 | 中国石油大学(华东) | Carbon and nitrogen co-doped titanium dioxide nano material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 温阳等，: "纳米二氧化钛粉体的制备及对染料脱色研究", 《辽宁化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112591792A (en) * | 2020-12-30 | 2021-04-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Simple preparation method of colored titanium dioxide for photocatalysis |
| CN112604688A (en) * | 2020-12-30 | 2021-04-06 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of ferroferric oxide loaded colored titanium dioxide for photocatalysis |
| CN112604688B (en) * | 2020-12-30 | 2023-02-14 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of ferroferric oxide loaded colored titanium dioxide for photocatalysis |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112079380A (en) | Method for preparing titanium dioxide | |
| CN106082317B (en) | A kind of preparation method of hollow hemisphere titanium dioxide | |
| CN112647287B (en) | Super-hydrophobic material with hierarchical coarse structure and preparation method and application thereof | |
| CN103803644B (en) | A kind of preparation method controlling titanium-based nano material product form and pattern | |
| CN103936027B (en) | Controlled SAPO-34 zeolitic material of colored shape of nanometer sheet assembling and preparation method thereof | |
| CN101717122A (en) | Method for preparing ferroferric oxide nano-piece through microwave method | |
| Truong et al. | Controlled synthesis of titania using water-soluble titanium complexes: A review | |
| CN106542557B (en) | A kind of preparation technology of nano-calcium carbonate | |
| CN111019152A (en) | Method for ultrasonic-assisted synthesis of zirconium-based metal organic framework material and product thereof | |
| CN107162047B (en) | A kind of preparation method of titanium dioxide hollow ball | |
| CN109879312A (en) | A kind of preparation method of photocatalyst of titanium dioxide nano-powder | |
| CN108687339A (en) | Titanium or titanium alloy spherical powder of low oxygen content and its preparation method and application | |
| CN102020283A (en) | Preparation method of silicon dioxide nano hollow sphere with adjustable inner diameter | |
| CN109534407A (en) | A kind of preparation method and applications of rodlike magnetic ferroferric oxide material | |
| CN110028074B (en) | Preparation method of spherical silicon dioxide | |
| Li et al. | Ordered macroporous titania photonic balls by micrometer-scale spherical assembly templating | |
| CN109574069B (en) | Carbon quantum dot induced titanium dioxide hierarchical nanostructure and preparation method thereof | |
| Zhu et al. | Adsorption properties of ZrO 2 hollow microboxes prepared using CaCO 3 cubes as templates | |
| CN111675238A (en) | Method for preparing multi-morphology nano zinc oxide by solid phase method | |
| CN110201655B (en) | One-step method for preparing hollow TiO2Method and application of nano-microspheres | |
| CN102936028A (en) | Method for preparing platy lanthanum hydroxide nanocrystalline through microwave-ultrasonic method | |
| CN104998629A (en) | SiO2-TiO2 composite nanomaterial of core-shell structure and preparation method and application thereof | |
| CN113651336A (en) | Silica microspheres and preparation method thereof | |
| CN106430222A (en) | Nanosilicon dioxide pellet and preparing method thereof | |
| CN103586013A (en) | Method for preparing wheat-ear-shaped nano ZnO photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220124 Address after: 232000 standardized workshop B1 of Zhenxing intelligent industrial park, Zhenxing South Road, Huainan Economic and Technological Development Zone, Anhui Province Applicant after: Huainan prospect new material Co.,Ltd. Address before: 230031 room 1305, Jinqian Plaza, 4680 Jinzhai South Road, Shushan District, Hefei City, Anhui Province Applicant before: Anhui Jingcheng New Material Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201215 |
|
| RJ01 | Rejection of invention patent application after publication |