KR101565477B1 - Preparing method of titanium oxide derivative - Google Patents

Abstract

Disclosed is a method for preparing a titanium oxide derivative by using a novel sulfuric acid method wherein the pressure and the temperature are adjusted in the process of hydrolyzing, forming and treating a titanium oxide derivative crystal or a conjugate thereof, thereby a size or a surface area of a nanoparticle crystal or a conjugate thereof are adjusted so that titanium oxide derivatives such as a meta-titanic acid and titanium dioxide, a hydrate thereof or a nanoparticle which can be formed chemically can be obtained in desired size and surface area. The present invention provides the method for preparing a titanium oxide derivative by using a sulfuric acid method which can prepare a titanium oxide derivative by hydrolyzing and calcinating a titanyl sulphate (TiOSO_4) solution formed by dissolving ilmenite to a sulfuric acid wherein the hydrolysis includes a step of applying pressure in relation to an external atmospheric pressure.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a titanium oxide derivative,

More particularly, the present invention relates to a method for producing a titanium oxide derivative such as titanium dioxide at a nanoparticle level by hydrolysis and calcination of a titanyl sulfate solution using a sulfuric acid method.

Titanium dioxide nanoparticles are used as raw materials for white dyestuffs. In addition, they are used as raw materials for various applications such as catalysts, photocatalysts, gas sensors, photoconductors, solar cells, ultraviolet screening agents, and coating materials in the chemical catalysts, electrochemical and photochemical industries Its value is very high. For example, titanium dioxide has an appropriate bonding strength to oxygen and is excellent in acid resistance and is used as an oxidation, reduction catalyst or carrier. In addition, titanium dioxide has high ultraviolet shielding properties and is thus used as a cosmetic raw material or a plastic surface coating agent, and is being used for the production of antibacterial agents, antifouling agents, and hydrophilic coating agents.

Titanium dioxide is produced by a sulfuric acid method which processes commercially raw ilmenite (ilmenite) with sulfuric acid and a chlorination method which treats raw rutile light with chlorine or hydrogen chloride in the presence of a reducing agent (mainly carbon). In the sulfuric acid method, the aluminate is dissolved in sulfuric acid, the iron ion is removed from the solution, and the solution is subjected to drying and calcination. The prepared titanium dioxide has mainly an anatase crystal type, and the sulfate ions and impurities remaining on the surface thereof are known to affect the titanium dioxide and cause a decrease in the reactivity and quality of the final product. On the other hand, the chlorine method for producing titanium dioxide by oxidation of titanium tetrachloride (TiCl ₄ ), which is a manufacturing intermediate, has a substantially homogeneous particle size distribution and contains a small amount of silicon (Si) and aluminum (Al) It is known that the purity of titanium dioxide is not high (Zhang Bang Jin, Graduate School of Kyonggi University, Department of Environmental Energy System Engineering, Master Thesis, 2008, pp. 60-62).

Titanium dioxide is known to have various crystal structures (crystalline or structural), such as anatase, rutile and brookite types. The use and performance of titanium dioxide is dependent on the crystal phase, shape and size of the particles. Very different. Particularly, the shape of the crystal and the size of the particles are known to have a great influence on the physicochemical, mechanical, electrical, magnetic and optical properties of the final product (X. Chen, SS Mao, J. Naosci. Nanotechnol. 6, 906-925). For example, the anatase type crystal form of titanium dioxide has been reported to exhibit the best photocatalytic activity and selective catalytic reduction (SCR) reactivity. It has a small particle size, homogeneous, well-controlled aggregation state, (Jang, Bang Jin, Graduate School of Kyonggi University, Department of Environmental Energy System Engineering, Master's Thesis, 2008, pp. 60-62).

However, due to the rapid reactivity of the titanium dioxide precursor, it is known that it is not easy to manufacture nanoparticles having controlled size, dispersion or specific surface area. Titanium dioxide nanoparticles prepared by a general method have a granular shape in which crystals are aggregated due to a faster reactivity than an individual crystalline granular form, and the particle size is much larger than the actual size due to the formation of granules. Therefore, it is common that the size of titanium dioxide nanoparticles is presented through particle size measurement by X-ray diffraction analysis (XRD) rather than the size of the granules produced. However, since granules are not well dispersed into individual particles, they are often present in the form of a complex or aggregate of strong affinity. In this case, titanium dioxide nanoparticles are originally When used in applications where a large surface area is required. Therefore, a method of adding silica, alumina, or an organic compound to control the size and specific surface area of the titanium dioxide nanoparticles has been proposed, but this is in fact added with impurities and may not be suitable depending on the intended use. Further, as a technique for homogenously controlling the titanium dioxide particles, additives such as an organic solvent such as alcohol, a surface substituting agent, a structural directing agent and the like, or a method of producing a cooling method at room temperature or lower are known (see International Patent Publication No. WO2011-149277 ). However, these methods may cause an increase in production cost and may not be easy to use in the titanium dioxide manufacturing process by the sulfuric acid method, and the additive may also act as an impurity which reduces the reactivity of the anatase titanium dioxide.

Therefore, it is possible to utilize the titanyl sulfate solution obtained by dissolving ilmenite in sulfuric acid in the existing titanium dioxide processing method and to use titanium dioxide nanoparticles obtained by dissolving the titanium dioxide nanoparticles It is necessary to develop a process capable of producing titanium dioxide nanoparticles having the necessary size and surface area according to the use purpose.

[Prior Patent Literature]

- Korean Registered Patent No. 1441436 (Nov.

- Chinese Patent Laid-Open Publication No. 103641164 (Mar. 19, 2014)

- Chinese Patent Publication No. 103073059 (May 31, 2013)

- International Patent Publication No. WO2013-147163 (Oct. 3, 2013).

- Korean Registered Patent No. 1065804 (September 9, 2011)

- Korean Registered Patent No. 1042018 (June 10, 2011)

- International Patent Publication No. WO 2005-121026 (Dec. 22, 2005)

- Korean Patent Registration No. 0430405 (Apr. 23, 2004)

- Korean Registered Patent No. 0374478 (Mar. 29, 2003)

- China Patent Publication No. 001541944 (November 23, 2004)

- Korean Registered Patent No. 0343395 (Jun. 24, 2002)

- International Patent Publication No. WO 2000-060130 (Oct. 12, 2000)

- Korean Registered Patent No. 0224732 (July 15, 1999)

- Korean Unexamined Patent Publication No. 1997-0059094 (Dec. 12, 1997)

- Korean Registered Patent Publication No. 0077674 (September 26, 1994)

- US Patent No. 5030439 (Jul. 9, 1991)

- Korean Patent Publication No. 1988-0003833 (May 30, 1988)

- Korean Registered Patent No. 0016154 (Apr. 24, 1984)

- Korean Unexamined Patent Publication No. 1983-0004159 (July 1983)

The present invention relates to a method for producing a titanium oxide derivative using a sulfuric acid method, which comprises controlling the size or surface area of a nanoparticle crystal or a binding substance by controlling the pressure and the temperature in hydrolysis, titanium oxide derivative crystal, And a method for producing the titanium oxide derivative by using a novel sulfuric acid method which enables to obtain nanoparticles which can be chemically formed in a desired size and surface area.

In order to solve the above problems, the present invention provides a method for producing a titanium oxide derivative by hydrolysis and calcination of a titanyl sulfate (TiOSO ₄ ) solution produced by dissolving ilmenite in sulfuric acid, The method for producing a titanium oxide derivative according to claim 1, wherein the hydrolysis comprises a pressurization step with respect to an external atmospheric pressure.

And the pressurization step is performed at a pressure of 1.05 to 2 times the external atmospheric pressure.

And the pressing step is performed at a temperature of 70 to 120 ° C.

And the pressing step is performed for 10 minutes to 4 hours.

And the hydrolysis is performed for 10 minutes to 4 hours at the temperature of 70 to 120 ° C. under the external atmospheric pressure before the pressurization step.

And the hydrolysis is repeated under the pressure and the atmospheric pressure, wherein the hydrolysis is performed for 1 to 6 hours.

And the hydrolysis is performed for 10 minutes to 4 hours at 70 to 120 ° C under the external atmospheric pressure after the pressing step.

And the hydrolysis and the pressurization step under the external atmospheric pressure are repeated, wherein the total hydrolysis is carried out for 1 to 6 hours.

And the calcination is performed at 200 to 500 ° C for 10 minutes to 3 hours.

Also, the titanium oxide derivative is at least one selected from the group consisting of titanium oxide, titanium oxide salt, metatitanic acid, hydrate of titanium oxide, and titanium dioxide.

Also, the titanium oxide derivative has a single crystal grain size of 1 to 25 nm.

The titanium oxide derivative has a specific surface area of 70 to 200 m < 2 > / g.

In order to produce titanic oxide derivatives such as titanium dioxide and metatitanic acid having a desired particle size or particle size and specific surface area in the process for producing titanium oxide derivatives by the sulfuric acid method, By controlling the amount of iron powder to be added and removing or adding iron ions in the titanyl sulfate solution, the F value (amount of sulfuric acid / amount of TiO ₂ ), Fe / TiO ₂ ratio, amount of TiO ₂ per liter, It is possible to control the average size and specific surface area of titanium oxide, which is an important factor of the quality standard for titanium oxide derivatives such as metatitanic acid and titanium dioxide, I do not.

The present invention relates to a method for preparing a titanium oxide derivative using a sulfuric acid method, in which a particle size and a specific surface area can be controlled without adjusting the water level by controlling the starting time of the pressure, the pressing time, the pressing temperature and the pressure value during the hydrolysis of the titanyl sulfate solution A new method can be provided in which the titanium oxide derivative such as nanocrystalline metatitanic acid, titanium dioxide or the like is adjusted to have a desired particle size and surface area through a heat treatment under optimal conditions and then formed into a very homogeneous state.

Further, according to the present invention, more uniform titanium oxide derivative particles can be produced by drying and polishing / pulverizing the titanium oxide derivative crystals such as titanium dioxide produced through hydrolysis from titanyl sulfate solution under specific pressurizing conditions under optimum conditions have.

FIGS. 1A to 1F are graphs showing XRD pattern diagrams of titanium dioxide nanoparticles prepared according to Examples 2, 5, 8, 11, 13, and 14, respectively,
1G and 1 H are graphs showing XRD reference pattern diagrams of anatase type titanium dioxide and XRD reference pattern diagrams of rutile titanium dioxide,
FIGS. 2A to 2F are SEM photographs of a 50,000-fold magnification of the titanium dioxide nanoparticles prepared according to Examples 1 to 6, respectively,
3A to 3F are SEM photographs of a 200,000 times magnification of the titanium dioxide nanoparticles prepared according to Examples 1 to 6, respectively,
4A to 4F are SEM photographs of a 50,000-fold magnification of the titanium dioxide nanoparticles prepared according to Examples 7 to 12, respectively,
5A-5F are SEM photographs of 200,000 times magnification of titanium dioxide nanoparticles prepared according to Examples 7-12 respectively,
6A and 6B are SEM photographs of a 50,000-fold magnification of the titanium dioxide nanoparticles prepared according to Examples 13 and 14, respectively,
7A and 7B are SEM photographs of 200,000 times magnification of titanium dioxide nanoparticles prepared according to Examples 13 and 14, respectively.

Hereinafter, preferred embodiments of the present invention will be described in detail. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. Throughout the specification, when an element is referred to as "including " an element, it means that it can include other elements, not excluding other elements, unless specifically stated otherwise.

The present inventors have found that in order to obtain a grain size or a specific surface area of a desired size in a titanium oxide derivative production method using a sulfuric acid method, the F value (amount of sulfuric acid / amount of TiO ₂ ), The ratio of Fe / TiO ₂ , and the amount of TiO ₂ per liter, it has been found that there is a limit to the mass production of TiO _{2 with} controlling the average size and specific surface area of the desired titanium oxide derivative. Surprisingly, The hydrolysis of the titanyl sulfate can be controlled to have the desired particle size and surface area by controlling the starting point of the pressure, the pressing time, the pressing temperature, the pressure value, etc., And arrived at the present invention.

Accordingly, the present invention provides a method for producing a titanium oxide derivative using a sulfuric acid method for producing a titanium oxide derivative by hydrolysis and calcination of a titanyl sulfate (TiOSO ₄ ) solution produced by dissolving ilmenite in sulfuric acid, Wherein the hydrolysis includes a pressurization step with respect to an external atmospheric pressure. In order to more clearly understand the features of the present invention prior to the description of the present invention, a process for manufacturing titanium dioxide using a conventional sulfuric acid method will be described in detail by way of example.

First, 93-96 wt.% Of the inorganic raw materials of titanium dioxide and sulfuric acid are heated to 155-190 ° C to dissolve the inorganic acid in sulfuric acid. At this time, sulfuric acid is used at 1 to 1.5 times as much as 1 ton of the ylmenite, and air is blown to oxidize Fe (II) of the ylmenite upon dissolution. As a result of the reaction as shown in Reaction Scheme 1, the unoxidized Fe (II) and the generated Ti (SO ₄ ) ₂ become crystals in the sulfuric acid solution as solid matter (solid matter).

[Reaction Scheme 1]

Thereafter, about three times as much water as the sum of the amount of the ylmenite is added to dissolve the solid material, and the waste sulfuric acid obtained after the hydrolysis described below is added to adjust the concentration. The solid state material is dissolved by the addition of water, through which a chemical reaction of the following reaction scheme 2 and scheme 3 occurs.

[Reaction Scheme 2]

[Reaction Scheme 3]

Then, iron (Fe) is reduced to Fe (III) according to the following Reaction Scheme 4 by adding iron powder to the solution obtained through Reaction Formula 2 and Reaction Formula 3.

[Reaction Scheme 4]

Thereafter, the crystals of ferrous sulfate and ferrous sulfate monohydrate (FeSO ₄ .7H ₂ O) are formed by vacuum decompression, and the ferrous sulfate crystals and impurities are removed by reduced pressure and microfiltration.

Thereafter, the titanyl sulfate solution was concentrated under reduced pressure while maintaining the temperature at 80 DEG C or lower, and the concentrated titanyl sulfate solution was subjected to hydrolysis at 95 to 105 DEG C for 3 to 8 hours to obtain meta titanic acid (Meta Titanic Acid, TiO (OH) ₂ ) crystals.

[Reaction Scheme 5]

The formed metatitanic acid is then filtered to remove sulfuric acid, and the metatitanic acid crystals are washed with distilled water two to three times, and washed with bleaching agent if necessary.

Thereafter, the washed metatitanic acid crystals are dried or calcined according to the intended use, followed by pulverization and polishing to complete the titanium dioxide product.

In the titanium dioxide manufacturing process using the conventional sulfuric acid method, hydrolysis is carried out by adjusting the F value, the Fe / TiO ₂ ratio and the amount of TiO ₂ per 1 liter of the titanyl sulfate solution before the hydrolysis unit process to obtain titanium tetrachloride crystals or titanium dioxide particles Production. Titanium dioxide or metatitanic acid is produced at the present time by setting the F value (sulfuric acid amount / TiO ₂ amount) of the titanyl sulfate solution to 1.75 to 1.85, the Fe / TiO ₂ ratio to 0.26 to 0.28 and the TiO ₂ amount per liter to 200 to 230 g do. The Fe / TiO ₂ ratio is also adjusted to 0.3 to 0.45. However, it is very difficult to precisely and uniformly control the crystal size, which is one of the most important elements of the quality standard of metatitanic acid or titanium dioxide, only by adjusting the process conditions for controlling the F value, the Fe / TiO ₂ ratio, and the amount of TiO ₂ per liter .

Thus, in the process of producing titanium dioxide using the conventional sulfuric acid method, the hydrolysis process produces the metatitanic acid crystal or powder by controlling the composition of the titanyl sulfate solution and the seed material for crystal formation, It is necessary to adjust the composition of the titanyl sulfate solution and adjust the reaction conditions to the titanyl sulfate solution in order to obtain the titanium (meth) acrylate or titanium dioxide crystal (or powder) or the binder. However, since there are process limitations such as additional variation factors due to differences in facilities environment or costs due to process changes, there is a limitation in the adjustment of these variables. Accordingly, the present invention overcomes the above- It is possible to form titanium dioxide particles in a very homogeneous state while adjusting the particle size and surface area to a desired value without performing the above parameter adjustment by performing the hydrolysis step and the subsequent heat treatment step in a narrow range with different pressure and temperature .

Generally, when the pressure is increased during the crystallization process, a small amount of small metatitanic acid crystals can be rapidly formed. In the present invention, the hydrolysis process for titanyl sulfate can be carried out by applying a pressure process, Titanium dioxide particles with different size particles and specific surface area can be prepared, followed by filtration to remove or recover sulfuric acid, followed by water or distilled water washing and any further treatment required, followed by calcination under optimal conditions to achieve the desired particle size and surface area So that the titanium dioxide particles can be formed in a very homogeneous state.

The present invention can also be applied to titanium oxide derivatives which can be produced through a sulfuric acid process in addition to titanium dioxide. That is, it is needless to say that the titanium oxide derivative can be selected from those known in the art. Examples of the titanium oxide derivative include titanium oxide, titanium oxide salt, metatitanic acid, hydrate of titanium oxide, and the like.

The pressurization step can be performed preferably at an atmospheric pressure of 1.05 to 2 atmospheric pressure, more preferably at a pressure of 1.1 to 1.45 times, and more preferably at a pressure of 1.15 to 1.4 atmospheres . If the pressurizing condition exceeds 2 times as much as the external atmospheric pressure, it may be difficult to form the titanium oxide derivative particles in a further homogeneous state with an increase in the process cost. Here, 'external atmospheric pressure' means the atmospheric pressure of the space in which the process reactor or process facility in which the titanium oxide derivative is manufactured by the sulfuric acid method is located.

In order to improve the reactivity upon hydrolysis of the titanyl sulfate solution at the above-mentioned pressure range and to easily adjust the particle size and specific surface area of the titanium oxide derivative to be produced, it is preferably carried out under a warm condition. That is, the pressing step is preferably performed at a temperature of 70 to 120 ° C, and the hydrolysis may be performed for 10 minutes to 4 hours. At this time, in view of the process efficiency, the reaction may be carried out at a temperature of 80 to 110 ° C for 10 minutes to 3 hours, and more preferably at a temperature of 90 to 105 ° C for 20 minutes to 2 hours.

In the present invention, the starting point of the pressing step is considered as means for further adjusting the size and specific surface area of the produced titanium oxide derivative particles and further improving the process efficiency. That is, in the present invention, it was confirmed that the size and specific surface area of the titanium oxide derivative particles can be more easily adjusted when the hydrolysis is further performed at a temperature and time within a certain range under the external atmospheric pressure before or after the pressurization step. Specifically, the hydrolysis may be carried out at a temperature of 70 to 120 ° C for 10 minutes to 4 hours under the external atmospheric pressure before or after the pressurization step. From the viewpoint of process efficiency, the hydrolysis under external atmospheric pressure is more preferably carried out at a temperature of 80 to 110 ° C for 10 minutes to 3 hours, more preferably at a temperature of 90 to 100 ° C for 20 minutes to 2 hours . Here, even when the hydrolysis is carried out while the hydrolysis is started under the atmospheric pressure at the external atmospheric pressure and the hydrolysis is carried out up to the above-mentioned pressurizing range, the effect similar to the case of performing the hydrolysis under external atmospheric pressure before or after the pressurizing step can be exerted.

In addition, when the hydrolysis process at the pressurization step and the external atmospheric pressure is repeated, the titanium oxide derivative having smaller particle size and particle size can be produced while slightly increasing the specific surface area of the finally produced titanium oxide derivative. That is, in the present invention, it is possible to repeat the hydrolysis under the pressurizing step and the atmospheric pressure under the atmospheric pressure, or the hydrolysis under the external atmospheric pressure and the pressurizing step. In this case, the total hydrolysis time is preferably 1 to 6 hours, more preferably 2 to 5 hours, and further preferably 3 to 4 hours. Further, the hydrolysis under repeated pressure and external atmospheric pressure may be carried out for 10 minutes to 3 hours, preferably 10 minutes to 2 hours, more preferably 10 minutes to 1 hour, and 10 to 30 minutes, respectively.

In the present invention, the calcination step is a step of warming the titanium oxide derivative crystals or the conjugate prepared under the above-described conditions of the pressurization and temperature conditions to finally produce nanoparticles of the titanium oxide derivative having the desired particle size and specific surface area. That is, in the present invention, it is preferable to have a desired grain size and specific surface area, but the target single crystal grain size is 1 to 25 nm, the specific surface area of the grain crystal is 70 to 200 m2 / g, preferably the grain size is 1.5 to 20 nm , The calcination process may be performed at 200 to 500 ° C for 10 minutes to 3 hours to prepare titanium oxide derivative nanoparticles having a specific surface area of 80 to 170 m 2 / g. At this time, the calcination process may be performed at 250 to 450 ° C for 1.5 to 2.5 hours in order to maximize homogeneity of the titanium oxide derivative finally produced.

The titanium oxide derivative crystals or complexes obtained through the calcination process are finally pulverized and polished to finally produce titanium oxide derivatives of the required standard.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. However, the following examples are illustrative of the present invention, and the present invention is not limited to the examples described below.

Example 1

(Titanyl sulfate solution having the same variables in the following examples was used) in a titanyl sulfate solution (F value of 1.7-1.9, Fe / TiO ₂ ratio of 0.2-0.5, TiO ₂ amount of 120-170 g per liter) Or an aqueous solution of sulfuric acid is added to dilute the solution to a conversion concentration of 170 g of TiO ₂ per liter, and the solution is heated to 95 ° C (at this time, a small amount of crystallization promoting seed may be added but may not be added) The mixture was hydrolyzed for 30 minutes while adjusting the temperature to 90 ° C. The pressure was maintained at 1.15 ± 0.1 times the atmospheric pressure for 1.5 hours and further hydrolyzed at normal atmospheric pressure for 30 minutes to form crystals (or crystals) The titanium dioxide nanoparticles were prepared by pulverization and polishing after performing post filtration, washing and post treatment as required and calcining at a temperature of 270 DEG C for about 2 hours.

Example 2

Titanium dioxide nanoparticles were prepared in the same manner as in Example 1, except that the calcination temperature was adjusted to 350 ° C in Example 1.

Example 3

Titanium dioxide nanoparticles were prepared in the same manner as in Example 1, except that the calcination temperature was adjusted to 450 캜 in Example 1.

Example 4

Titanium dioxide nanoparticles were prepared in the same manner as in Example 1, except that the pressurization temperature was adjusted to 105 ° C in Example 1.

Example 5

Titanium dioxide nanoparticles were prepared in the same manner as in Example 2, except that the pressurization temperature was adjusted to 105 ° C in Example 2.

Example 6

Titanium dioxide nanoparticles were prepared in the same manner as in Example 3, except that the pressurization temperature was adjusted to 105 캜 in Example 3.

Example 7

Titanium dioxide nanoparticles were prepared in the same manner as in Example 1, except that the pressurizing pressure in Example 1 was adjusted to 1.40 占 0.1 atmospheric pressure.

Example 8

Titanium dioxide nanoparticles were prepared in the same manner as in Example 2, except that the pressure in Example 2 was adjusted to 1.40 占 0.1 atmospheric pressure.

Example 9

Titanium dioxide nanoparticles were prepared in the same manner as in Example 3, except that the pressure in Example 3 was adjusted to 1.40 占 0.1 atmospheric pressure.

Example 10

Titanium dioxide nanoparticles were prepared in the same manner as in Example 4, except that the pressure in Example 4 was adjusted to 1.40 占 0.1 atmospheric pressure.

Example 11

Titanium dioxide nanoparticles were prepared in the same manner as in Example 5, except that the pressure in Example 5 was adjusted to 1.40 占 0.1 atmospheric pressure.

Example 12

Titanium dioxide nanoparticles were prepared in the same manner as in Example 6, except that the pressure in Example 6 was adjusted to 1.40 占 0.1 atmospheric pressure.

Example 13

While heating the titanyl sulfate solution, water or an aqueous solution of sulfuric acid is added to dilute the solution to a conversion concentration of TiO ₂ per liter of 170 g, and the solution is heated to 95 ° C (the seed for promoting crystallization may be added in small amounts but it may be omitted. ), The hydrolysis was started at 95 ° C under a normal atmospheric pressure, the temperature of the solution was adjusted to 105 ° C, the pressure was increased to 1.15 ± 0.1 atmospheric pressure and hydrolysis was carried out for 20 minutes (Step 1) The hydrolysis was carried out for 20 minutes under reduced pressure (step 2). Then, Step 1 and Step 2 were repeated to complete a total hydrolysis time of 160 minutes, followed by filtration, washing, and necessary treatments, followed by calcination at 350 ° C for about 2 hours, followed by pulverization and polishing to prepare titanium dioxide nanoparticles.

Example 14

Titanium dioxide nanoparticles were prepared in the same manner as in Example 13 except that the pressurizing pressure of Step 1 in Example 13 was adjusted to 1.40 占.

Test Example 1

(SU-70 FE-SEM, Hitachi High Technologies) in order to confirm the overall morphology of the titanium dioxide nanoparticles prepared according to the above examples, and X-ray diffraction XRD (PANalytical X'Pert X-ray diffractometer system) was used. Particle size and particle size homogeneity were measured using a nano particle size analyzer (Zetasizer Nano ZS90) ASAP 2020, Micometitics) was used to measure the specific surface area (BET).

Figs. 1A to 1F show XRD pattern diagrams of titanium dioxide nanoparticles prepared according to Examples 2, 5, 8, 11, 13, and 14, respectively. Fig. 1G and Fig. 1H show anatase titanium dioxide And an XRD reference pattern of rutile type titanium dioxide. 2A to 2F show SEM photographs of the titanium dioxide nanoparticles prepared according to Examples 1 to 6 at a magnification of 50,000 times, and FIGS. 3A to 3F show titanium dioxide nanoparticles prepared according to Examples 1 to 6, respectively. SEM photographs of 200,000 times magnification of the nanoparticles were shown. Figs. 4A to 4F show SEM photographs of 50,000 times magnification of the titanium dioxide nanoparticles prepared according to Examples 7 to 12, respectively, and FIGS. 5A to 5F SEM photographs of 200,000 times magnification of the titanium dioxide nanoparticles prepared according to Examples 7 to 12 are shown respectively. Figs. 6A and 6B show SEM photographs of the titanium dioxide nanoparticles prepared according to Examples 7 to 12 at a magnification of 50,000 times SEM photographs are shown in FIGS. 7A and 7B. FIGS. 7A and 7B show SEM photographs of the titanium dioxide nanoparticles prepared according to Examples 13 and 14 at a magnification of 200,000 times, respectively. Table 1 below shows the single crystal grain size (XRD), specific surface area (BET) and binder particle size (d50) of the titanium dioxide nanoparticles prepared according to each example.

Titanium dioxide nanoparticles (Examples 1 to 6) prepared under the pressurization conditions of 1.15 ± 0.1 times the atmospheric pressure as compared with the external atmospheric pressure generally have a particle diameter in the range of 3.0 to 15.0 nm and a specific surface area in the range of 80.0 to 170.0 m 2 / g ). It can be seen that particles having a relatively large particle diameter are formed at 105 DEG C (Examples 4 to 6) in comparison with the case where the pressing temperature at the hydrolysis is 90 DEG C (Examples 1 to 3). In addition, when hydrolysis, filtration and washing are followed by heating (calcination) treatment, it can be seen that particles having a relatively large particle size are formed as the treatment temperature is higher. In addition, all of the nanoparticles produced exhibited typical anatase-type XRD patterns (see FIGS. 1A and 1B), and on SEM photographs, the nanoparticles formed irregularly shaped solid granules of homogeneous spherical particles within 15 nm (See Figs. 2 and 3).

Next, in the case of the titanium dioxide nanoparticles (Examples 7 to 12) produced under the pressurization conditions of 1.40 ± 0.1 times of the atmospheric pressure relative to the external atmospheric pressure, the titanium dioxide nanoparticles (Examples 7 to 12) Nanoparticles. (BET) in the range of 90.0 to 170.0 m < 2 > / g and in the case of the temperature of hydrolysis at 90 DEG C (Examples 7 to 9) and at 105 DEG C Examples 10 to 12) were formed into particles having substantially similar particle diameters, and the cases of heating (calcining) treatment after hydrolysis, filtration and washing were examined in a treatment group at 450 占 폚 (Examples 9 and 12) (Examples 7 and 10) or 350 占 폚 treated groups (Examples 8 and 11). In addition, all of the nanoparticles produced exhibited typical anatase-type XRD patterns (see FIG. 1C and FIG. 1D), and on the SEM photographs, nanoparticles formed irregularly shaped solid granules of homogeneous spherical particles within 10 nm (See Figs. 4 and 5).

Titanium dioxide nanoparticles prepared by repeating the pressurization step and the hydrolysis under the external atmospheric pressure (Examples 13 and 14), titanium dioxide nanoparticles prepared by applying pressurization conditions at 1.15 ± 0.1 atm example 13) the nanoparticles produced are XRD average particle size 6.2nm, a specific surface area (BET) without performing the 173.10㎡ / g and a conjugate particle size (d ₅₀₎ is as 695nm, the similar hydrolysis conditions being the condition repeats ( The particle size and the particle size and thus the large specific surface area were smaller than those of Example 5). In addition, the titanium dioxide nanoparticles produced by applying a pressurized condition by 1.40 ± 0.1 times the atmospheric pressure (Example 14) has an average particle size of 5.4nm The XRD, surface area (BET) is 167.60㎡ / g and a conjugate particle size (d ₅₀₎ is 783nm And the hydrolysis conditions were not repeated, and the specific surface area was similar to that of the prepared nanoparticles (Example 11), but it was confirmed that the nanoparticles were small in particle size and particle size. On the other hand, in the case of the same conditions except for the pressure, the nanoparticles prepared under the pressurization conditions of 1.15 ± 0.1 times of the atmospheric pressure (Example 13) were superior to the nanoparticles prepared under the pressurization conditions of 1.40 ± 0.1 times of the atmospheric pressure And a relatively large particle size was exhibited. The XRD analysis of the prepared nanoparticles showed a typical anatase structure (see FIGS. 1E and 1F). On the SEM photograph, the nanoparticles form an irregular shaped solid granule composed of very small homogeneous spherical particles Respectively.

The preferred embodiments of the present invention have been described in detail above. It will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Accordingly, the scope of the present invention is defined by the appended claims rather than the foregoing detailed description, and all changes or modifications derived from the meaning, range, and equivalence of the claims are included in the scope of the present invention Should be interpreted.

Claims (12)

A method for preparing a titanium oxide derivative using a sulfuric acid method for producing a titanium oxide derivative by hydrolysis, drying or calcination of a titanyl sulfate (TiOSO ₄ ) solution produced by dissolving ilmenite in sulfuric acid,
Wherein the hydrolysis comprises a pressurization step to an external atmospheric pressure,
The hydrolysis is carried out for 10 minutes to 4 hours at the temperature of 70 to 120 ° C under the external atmospheric pressure before the pressurization step or the hydrolysis is performed for 10 minutes to 4 hours at the temperature of 70 to 120 ° C under the external atmospheric pressure after the pressurization step, Gt; to < RTI ID = 0.0 > 1, < / RTI > The method according to claim 1,
Wherein the pressurization step is performed at a pressure of 1.05 to 2 times the external atmospheric pressure. The method according to claim 1,
Wherein the pressing step is performed at a temperature of 70 to 120 ° C. The method according to claim 1,
Wherein the pressing step is performed for 10 minutes to 4 hours. delete The method according to claim 1,
Wherein the hydrolysis is performed under the atmospheric pressure and the pressurization step when the hydrolysis is performed under the external atmospheric pressure before the pressurization step, wherein the total hydrolysis is performed for 1 to 6 hours. delete The method according to claim 1,
Wherein the hydrolysis under external atmospheric pressure and the pressurization step are repeated when hydrolysis is carried out under the external atmospheric pressure after the pressurization step, wherein the total hydrolysis is performed for 1 to 6 hours. The method according to claim 1,
Wherein the drying or calcination is performed at 200 to 500 ° C for 10 minutes to 3 hours. The method according to any one of claims 1 to 4, 6, 8, and 9,
Wherein the titanium oxide derivative is at least one selected from the group consisting of titanium oxide, titanium oxide salt, metatitanic acid, hydrate of titanium oxide, and titanium dioxide. The method according to any one of claims 1 to 4, 6, 8, and 9,
Wherein the titanium oxide derivative is formed of nanoparticles and the size of the nanoparticles is 1 to 25 nm on the basis of the particle diameter of a single crystal through X-ray diffraction analysis (XRD) analysis. The method according to any one of claims 1 to 4, 6, 8, and 9,
Wherein the average particle size per unit weight of the particles formed by aggregation of nanoparticles and nanoparticles of the titanium oxide derivative after the drying or calcination is 70 to 200 m < 2 > / g.

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