CN113979471B - Synthetic method of rutile type titanium dioxide nano-composite - Google Patents
Synthetic method of rutile type titanium dioxide nano-composite Download PDFInfo
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Abstract
The invention discloses a synthetic method of a rutile type titanium dioxide nano-composite, which comprises the following steps: 1. TiCl is added to the mixture 4 Dissolving the precursor in a polar solvent to obtain TiOCl 2 A solution; 2. weighing alpha-Al-containing material 2 O 3 Al of (2) 2 O 3 Placing the solid powder in TiOCl 2 The solution is obtained into solid powder after impregnation; 3. and drying and roasting to obtain the rutile type titanium dioxide nano-composite. The invention adopts the alloy containing alpha-Al 2 O 3 Al of (2) 2 O 3 Impregnating a precursor solution with a solid powder using alpha-Al in the solid powder 2 O 3 Is formed by the small crystal grain rutile TiO of the immersed solid powder in the drying process 2 As crystal nucleus, other TiOCl is combined with roasting process 2 The precursor is totally converted into rutile TiO 2 Solves the defects of high energy consumption, large water consumption, complicated steps, large wastewater discharge, difficult industrial scale-up preparation and the like of the traditional rutile type titanium dioxide preparation method.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a synthetic method of a rutile titanium dioxide nano-composite.
Background
Titanium dioxide has three crystal structures of rutile, anatase and brookite, wherein the rutile is the most thermodynamically stable state, and the good physicochemical properties of the titanium dioxide enable the titanium dioxide to be used in catalysis, energy storage, antibiosis and sensorsAnd the like, and is widely applied in the fields of the like. Currently industrially rutile TiO 2 The large-scale synthesis method of (2) is divided into a chlorination method and a sulfuric acid method, and the two methods are subjected to a phase inversion process from amorphous to anatase to rutile through high-temperature solid-phase reaction. Typically, anatase to rutile TiO 2 For example, the meta-titanic acid reported in Chinese patent CN97120161.7 needs to be transformed at 800-900 ℃ to obtain titanium dioxide with rutile content of more than 95%. In the preparation process of the traditional rutile type titanium dioxide, the high-temperature roasting has huge energy consumption and is extremely easy to cause rutile TiO 2 Aggregation and sintering of particles, often with specific surface areas of less than 10m 2 /g。
It was found that anatase titania can be converted to the rutile form at low temperatures as the diameter of the titania decreases to nanometer size. The preparation of rutile type nano titanium dioxide by low-temperature liquid phase avoids the high-temperature crystal form conversion process, and becomes a research hot spot (Journal of the American Ceramic Society,1999,82 (4): 927-932 and langmuir,2003,19 (3): 967-971) for preparing the rutile type titanium dioxide with high specific surface area. Chinese patent CN02152186.7 discloses hydrolysis of TiCl by room temperature 4 The aqueous solution is crystallized for 2 to 3 days at a low temperature of between 25 and 80 ℃ to prepare the TiO with a rutile phase structure 2 . Chinese patent CN00119033.4 discloses the use of beta-cyclodextrin, siO 2 、Al 2 O 3 Or different crystal forms of TiO 2 As seed crystal, tiCl is hydrolyzed at room temperature 4 Precursor, one-step synthesis of large specific surface area nano rutile type TiO 2 . Chinese patent CN105879866 discloses a process for preparing rutile-type nano titanium dioxide by hydrothermal reaction of tetrabutyl titanate as precursor in aqueous solution containing concentrated hydrochloric acid and hydrogen peroxide at 170-230 ℃. However, no matter the low-temperature hydrolysis method or the hydrothermal method, the steps of low-concentration precursor, nano titanium dioxide liquid phase separation, washing and the like make the preparation method with low synthesis efficiency, high energy consumption and high wastewater discharge in the liquid phase synthesis process.
Titanium dioxide is often not pure TiO when used in applications such as catalysis, photoelectrochemical cells, bactericides, and the like 2 One, one (a)Typically in the form of a complex. Chinese patent CN200680022449.1 reports a complex of rutile titanium dioxide and α -alumina prepared by mixing titanium dioxide and α -alumina, molding, and calcining to form a bar-shaped composite support for RuO 2 A carrier for a supported catalyst. However, the method has long steps, needs to prepare rutile titanium dioxide first, and is unfavorable for controlling TiO by a simple mixed roasting method 2 Is a size of (c) a. In-situ synthesis of rutile type titanium dioxide compound is more beneficial to control of TiO 2 Dispersibility, son Hoang et al (Catalysis Today 2019,320,2-10) reported that a composite of rutile type titanium dioxide and cordierite honeycomb carrier was prepared by immersing the cordierite carrier in a mixed solution of tetrabutyl titanate, titanium tetrachloride, 37% hydrochloric acid, toluene, solvothermal reaction at 150 ℃, and then calcining at 500 ℃ to obtain a composite carrier of rutile type titanium dioxide and cordierite honeycomb grown in situ. Yener, H.B et al (Separation and Purification Technology 2017,173,17-26.) synthesized in situ a complex of rutile titanium dioxide and clinoptilolite by a low temperature hydrolysis process. However, the low-temperature hydrolysis method and the hydrothermal method adopted for in-situ synthesis of the rutile type titanium dioxide compound are similar to those for preparing pure titanium dioxide, and the defects of multiple steps, low synthesis efficiency, high energy consumption, high wastewater discharge and the like still exist.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a synthetic method of a rutile titanium dioxide nanocomposite aiming at the defects of the prior art. The method adopts a catalyst containing alpha-Al 2 O 3 Al of (2) 2 O 3 Impregnating a precursor solution with a solid powder using alpha-Al in the solid powder 2 O 3 Is formed by the small crystal grain rutile TiO of the immersed solid powder in the drying process 2 As crystal nucleus, other TiOCl is combined with roasting process 2 The precursor is totally converted into rutile TiO 2 The rutile type titanium dioxide nano-composite is ensured to be obtained.
In order to solve the technical problems, the invention adopts the following technical scheme: a method for synthesizing a rutile titanium dioxide nanocomposite, comprising the steps of:
step one, tiCl is put into ice bath condition 4 The precursor is dissolved in a polar solvent to prepare TiOCl 2 A solution;
step two, weighing the alpha-Al-containing material by adopting an immersion method 2 O 3 Al of (2) 2 O 3 Placing the solid powder in TiOCl obtained in the first step 2 Impregnating the solution to obtain impregnated solid powder;
and thirdly, drying the impregnated solid powder obtained in the second step for 6-24 hours at 60-120 ℃, and roasting for 2-5 hours at 400-500 ℃ to obtain the rutile type titanium dioxide nano-composite.
TiCl is firstly put into the invention 4 The precursor is dissolved in a polar solvent to prepare TiOCl 2 Solution and then impregnate with alpha-Al containing 2 O 3 Al of (2) 2 O 3 And (3) drying and roasting the solid powder in sequence to obtain the rutile type titanium dioxide nano-composite. The method uses Al 2 O 3 alpha-Al in solid powder 2 O 3 Is formed by the small crystal grain rutile TiO of the immersed solid powder in the drying process 2 As crystal nucleus, other TiOCl is combined with roasting process 2 The precursor is totally converted into rutile TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the In the synthesis process, the rutile titanium dioxide can be obtained at low temperature by adopting an impregnation method in combination with drying and roasting, a high-temperature crystal transformation process is not needed, meanwhile, the rutile titanium dioxide nano-composite is synthesized in situ, the uniform dispersion of the rutile titanium dioxide in the nano-composite is facilitated, and the specific surface area of the rutile titanium dioxide nano-composite is increased. Meanwhile, the synthesis method has few steps, the adopted high-concentration precursor solution reduces the water consumption, the roasting process saves energy consumption compared with the traditional rutile synthesis method, is suitable for industrial production, and overcomes the defects of high energy consumption, large water consumption, complicated steps, more wastewater discharge, difficult industrial scale-up preparation and the like in the existing liquid phase method and high-temperature solid phase method for preparing rutile type titanium dioxide.
The method for synthesizing the rutile type titanium dioxide nano-composite is characterized in that the polar solvent in the first step is deionized water or a mixed solvent consisting of deionized water and methanol or/and ethanol.
The synthetic method of the rutile type titanium dioxide nano-composite is characterized in that the TiOCl in the first step 2 The concentration of the solution is 3mol/L to 5mol/L. The invention is realized by controlling the precursor TiOCl 2 The concentration of the solution ensures the TiO in the product 2 And TiOCl is avoided 2 Too high a concentration of the solution results in volatilization, which is detrimental to the smooth progress of the synthesis.
The synthetic method of the rutile type titanium dioxide nano-composite is characterized in that the impregnation method in the second step is an isovolumetric impregnation method. The invention has simple process, can be carried out by adopting a conventional isovolumetric impregnation method, does not need solid-liquid separation, and reduces the subsequent operation steps.
The synthetic method of the rutile type titanium dioxide nano-composite is characterized in that the impregnation in the second step is one-time impregnation or multiple-time impregnation. The invention effectively controls the TiO of the rutile type titanium dioxide nano-composite by controlling the times of impregnation 2 And the compounding amount is simple to operate and easy to control.
The synthesis method of the rutile type titanium dioxide nano-composite is characterized in that the step two comprises the step two of containing alpha-Al 2 O 3 Al of (2) 2 O 3 alpha-Al in solid powder 2 O 3 The mass content of (2) is more than 80%. The invention is realized by controlling alpha-Al 2 O 3 The mass content of (2) effectively ensures the TiO in the product 2 Titanium dioxide of rutile type and TiO of anatase crystal form is avoided 2 Is generated.
The above-mentioned synthetic method of rutile titanium dioxide nanocomposite, characterized in that in step three, the rutile TiO of the rutile titanium dioxide nanocomposite is of the crystal form 2 With alpha-Al 2 O 3 The mass ratio of (2) is 4-40: 100. the rutile type titanium dioxide nano-composite synthesized by the inventionHas enough rutile crystal form TiO 2 Ensures the use function and simultaneously avoids TiO 2 Too high a content of TiO in the composite is difficult to control 2 Is a crystal grain size of (c).
The synthetic method of the rutile type titanium dioxide nano-composite is characterized in that the grain size of titanium dioxide in the rutile type titanium dioxide nano-composite in the step three is smaller than 20nm, and the proportion of the rutile crystal form is 100%. The rutile type titanium dioxide nano-composite has small crystal grain size of titanium dioxide, is beneficial to increasing the specific surface area and improving the use performance in the application fields of catalysis, energy storage and the like.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts the alloy containing alpha-Al 2 O 3 Al of (2) 2 O 3 Impregnating a precursor solution with a solid powder using alpha-Al in the solid powder 2 O 3 Is formed by the small crystal grain rutile TiO of the immersed solid powder in the drying process 2 As crystal nucleus, other TiOCl is combined with roasting process 2 The precursor is totally converted into rutile TiO 2 The rutile type titanium dioxide nano-composite is ensured to be obtained.
2. The invention adopts the dipping method to combine drying and roasting, can obtain rutile titanium dioxide at low temperature, does not need a high-temperature crystal transformation process, simultaneously synthesizes the rutile titanium dioxide nano-composite in situ, is favorable for the uniform dispersion of the rutile titanium dioxide in the nano-composite, increases the specific surface area of the rutile titanium dioxide, has simple process and easy control, and solves the defects of high energy consumption, large water consumption, complicated steps, multiple wastewater discharge, difficult industrial scale-up preparation and the like of the traditional preparation method of the rutile titanium dioxide.
3. The invention prepares TiOCl by controlling 2 The concentration of the solution and the times of impregnation effectively control the content of the rutile type titanium dioxide in the nano-composite, thereby controlling the composition and the application performance of the rutile type titanium dioxide composite.
4. The dipping method adopted by the invention has the advantages of less steps, less water consumption, low energy consumption, short period and high yield, and is suitable for industrial production.
5. TiO in the rutile type titanium dioxide nano composite synthesized by the invention 2 The crystal is of a pure rutile crystal form, has a grain size smaller than 20nm, and is beneficial to improving the application performance.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 shows the X-ray diffraction patterns of the composites 1 to 4 prepared in examples 1 to 4 of the present invention.
FIG. 2 is an X-ray diffraction pattern of the composites C-1 to C-3 prepared in comparative examples 1 to 3 according to the present invention.
Detailed Description
The crystal forms of the compounds 1-4 and the compounds C-1 and C-2 synthesized in the examples 1-4 and the comparative examples 1-2 are measured by using a Holland Panac X' Pert Powder type multifunctional Powder X-ray diffractometer, and the operation conditions of the diffractometer are as follows: cuK alpha ray source, working voltage 40kV, working current 40mA, step length 0.02 DEG, scanning range 2 theta=10 DEG-80 DEG, scanning rate 5 DEG/min, and rutile type TiO 2 The grain size is calculated from the diffraction peak of the (110) crystal face by a Schle formula; rutile type TiO in composite 2 With alpha-Al 2 O 3 The mass ratio of (2) is quantified by a RIR method.
Example 1
The embodiment comprises the following steps:
step one, tiCl is put into ice bath condition 4 The precursor is dissolved in deionized water to prepare 3mol/L TiOCl 2 A solution;
step two, weighing 30g of alpha-Al 2 O 3 80% by mass of Al 2 O 3 Solid powder, put in 25g TiOCl obtained in step one 2 Carrying out equal volume impregnation on the solution to obtain impregnated solid powder;
and step three, drying the impregnated solid powder obtained in the step two at 60 ℃ for 6 hours, and roasting at 400 ℃ for 2 hours to obtain a rutile type titanium dioxide nano-composite, which is denoted as a composite 1.
Through detection, rutile crystal form TiO in the compound 1 obtained in the embodiment 2 The ratio of (C) is 100%, tiO 2 The grain size was 9.3nm, and the TiO in composite 1 2 With alpha-Al 2 O 3 The mass ratio is 15:100.
the polar solvent in step one of this embodiment may be deionized water, methanol, and ethyl according to 20:1:1 volume ratio.
Example 2
The embodiment comprises the following steps:
step one, tiCl is put into ice bath condition 4 The precursor is dissolved in a mixed solvent to prepare 3mol/L TiOCl 2 A solution; the mixed solvent is prepared from deionized water and methanol according to a ratio of 10:1, mixing the mixture in a volume ratio;
step two, weighing 40g of alpha-Al 2 O 3 95% by mass of Al 2 O 3 Solid powder, placing 13g of TiOCl obtained in step one 2 Carrying out equal volume impregnation on the solution to obtain impregnated solid powder;
and step three, drying the impregnated solid powder obtained in the step two for 10 hours at 110 ℃, and roasting for 5 hours at 500 ℃ to obtain a rutile type titanium dioxide nano-composite, which is denoted as a composite 2.
Through detection, rutile crystal form TiO in the compound 2 obtained in the embodiment 2 The ratio of (C) is 100%, tiO 2 The grain size was 11.1nm, and the TiO in composite 2 2 With alpha-Al 2 O 3 The mass ratio is 4:100.
example 3
The embodiment comprises the following steps:
step one, tiCl is put into ice bath condition 4 The precursor is dissolved in deionized water to prepare 4mol/L TiOCl 2 A solution;
step two, weighing 30g of alpha-Al 2 O 3 80% by mass of Al 2 O 3 Solid powder, put in 25g TiOCl obtained in step one 2 Carrying out equal volume impregnation on the solution to obtain impregnated solid powder;
step three, drying the impregnated solid powder obtained in the step two for 10 hours at 120 ℃, and roasting for 2 hours at 400 ℃ to obtain a compound intermediate;
step four, placing 20g of the compound intermediate obtained in the step three in 13g of TiOCl obtained in the step one 2 Carrying out equal volume impregnation on the solution;
and step five, drying the compound intermediate subjected to isovolumetric impregnation in the step four for 10 hours at the temperature of 110 ℃, and roasting for 2 hours at the temperature of 400 ℃ to obtain a rutile type titanium dioxide nano-compound, which is denoted as a compound 3.
Through detection, rutile crystal form TiO in the compound 3 obtained in the embodiment 2 The ratio of (C) is 100%, tiO 2 The grain size was 8.2nm, and TiO in Compound 3 2 With alpha-Al 2 O 3 The mass ratio is 40:100.
example 4
The embodiment comprises the following steps:
step one, tiCl is put into ice bath condition 4 The precursor is dissolved in a mixed solvent to prepare TiOCl with the concentration of 5mol/L 2 A solution; the mixed solvent is formed by mixing deionized water and ethanol according to the volume ratio of 20:1;
step two, weighing 30g of alpha-Al 2 O 3 80% by mass of Al 2 O 3 Solid powder, put in 25g TiOCl obtained in step one 2 Carrying out equal volume impregnation on the solution to obtain impregnated solid powder;
and step three, drying the impregnated solid powder obtained in the step two for 24 hours at 110 ℃, and roasting for 3 hours at 500 ℃ to obtain a rutile type titanium dioxide nano-composite, which is denoted as a composite 4.
Through detection, rutile crystal form TiO in the compound 4 obtained in the embodiment 2 The ratio of (C) is 100%, tiO 2 The grain size was 9.6nm, and the TiO in composite 4 2 With alpha-Al 2 O 3 The mass ratio is 26:100.
comparative example 1
The comparative example comprises the following steps:
step one, tiCl is put into ice bath condition 4 The precursor is dissolved in deionized water to prepare 3mol/L TiOCl 2 A solution;
step two, weighing 100g of gamma-Al 2 O 3 Powder, tiOCl obtained in step one, 90g, was placed in an isovolumetric impregnation 2 Impregnating the solution to obtain impregnated solid powder;
and step three, drying the impregnated solid powder obtained in the step two for 2 hours at the temperature of 110 ℃, and roasting for 2 hours at the temperature of 400 ℃ to obtain a titanium dioxide nano-composite, which is marked as a composite C-1.
Comparative example 2
The comparative example comprises the following steps:
step one, tiCl is put into ice bath condition 4 The precursor is dissolved in deionized water to prepare 3mol/L TiOCl 2 A solution;
step two, weighing 50g of SiO 2 Powder, placing the powder in 200g of TiOCl obtained in the step one by adopting an isovolumetric impregnation method 2 Impregnating the solution to obtain impregnated solid powder;
and step three, drying the impregnated solid powder obtained in the step two for 24 hours at the temperature of 110 ℃, and roasting for 2 hours at the temperature of 400 ℃ to obtain a titanium dioxide nano-composite, which is marked as a composite C-2.
Comparative example 3
The comparative example comprises the following steps:
step one, tiCl is put into ice bath condition 4 The precursor is dissolved in deionized water to prepare 3mol/L TiOCl 2 A solution;
step two, weighing 50g of alpha-Al 2 O 3 Al with a mass content of 50% 2 O 3 Solid powder, tiOCl obtained in step one 25g was placed by isovolumetric impregnation 2 Impregnating the solution to obtain impregnated solid powder;
and step three, drying the impregnated solid powder obtained in the step two for 2 hours at the temperature of 110 ℃, and roasting for 2 hours at the temperature of 400 ℃ to obtain a titanium dioxide nano-composite, which is marked as a composite C-3.
FIG. 1 shows the X-ray diffraction patterns of the composites 1 to 4 prepared in examples 1 to 4 of the present invention, and it is understood from FIG. 1 that the composites 1 to 4 prepared by the method of the present invention are rutile type titanium dioxide nanocomposites with a rutile crystal form of 100%.
FIG. 2 is an X-ray diffraction pattern of the composites C-1 to C-3 prepared in comparative examples 1 to 3 according to the present invention, and it is understood from FIG. 2 that gamma-Al is used 2 O 3 Powder or SiO 2 The compound C-1 and C-2 prepared by the powder are anatase titanium dioxide and alpha-Al is adopted 2 O 3 Al with a mass content of 50% 2 O 3 Diffraction peak of anatase titanium dioxide and alpha-Al in compound C-3 prepared from solid powder 2 O 3 Coincident, no significant rutile titanium dioxide diffraction peak was observed.
As can be seen by comparing FIGS. 1 and 2, the present invention employs a composition containing alpha-Al 2 O 3 Al of (2) 2 O 3 Synthesis method of solid powder impregnation, and Al 2 O 3 The solid powder has higher alpha-Al 2 O 3 The mass content ensures the complete conversion formation of the rutile titanium dioxide and effectively realizes the preparation of the rutile titanium dioxide nano-composite.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.
Claims (7)
1. A method for synthesizing a rutile titanium dioxide nanocomposite, comprising the steps of:
step one, tiCl is put into ice bath condition 4 The precursor is dissolved in a polar solvent to prepare TiOCl 2 A solution;
step two, adoptingWeighing alpha-Al content by dipping method 2 O 3 Al of (2) 2 O 3 Placing the solid powder in TiOCl obtained in the first step 2 Impregnating the solution to obtain impregnated solid powder; the alpha-Al-containing 2 O 3 Al of (2) 2 O 3 alpha-Al in solid powder 2 O 3 The mass content of (2) is more than 80%;
and thirdly, drying the impregnated solid powder obtained in the second step at 60-120 ℃ for 6-24 hours, and roasting at 400-500 ℃ for 2-5 hours to obtain the rutile type titanium dioxide nanocomposite.
2. The method of claim 1, wherein the polar solvent in the first step is deionized water or a mixed solvent of deionized water and methanol or/and ethanol.
3. The method of claim 1, wherein the TiOCl in step one is a compound of rutile titanium dioxide 2 The concentration of the solution is 3mol/L to 5mol/L.
4. The method of claim 1, wherein the impregnating method in the second step is an isovolumetric impregnating method.
5. The method of claim 1, wherein the impregnating in the second step is one or more impregnations.
6. The method of claim 1, wherein the rutile TiO 2 nanocomposite of step three is rutile TiO 2 nanocomposite 2 With alpha-Al 2 O 3 The mass ratio of (2) is 4-40: 100.
7. the method for synthesizing a rutile titanium dioxide nanocomposite according to claim 1, wherein the crystal grain size of titanium dioxide in the rutile titanium dioxide nanocomposite in the step three is less than 20nm, and the proportion of rutile crystal is 100%.
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