CN107531506B - Process for producing titanium oxide derivative - Google Patents
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- CN107531506B CN107531506B CN201580078315.0A CN201580078315A CN107531506B CN 107531506 B CN107531506 B CN 107531506B CN 201580078315 A CN201580078315 A CN 201580078315A CN 107531506 B CN107531506 B CN 107531506B
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Abstract
A process for preparing titanium oxide derivatives using a novel sulfuric acid process is disclosedA method in which the size or surface area of the nanoparticle crystals or agglomerates is adjusted by controlling the pressure and temperature in the steps of hydrolysis, and formation and treatment of titanium oxide derivative crystals or agglomerates, a titanium oxide derivative having a desired size and surface area, such as metatitanic acid or titanium dioxide, a hydrate thereof or a material chemically formable nanoparticle thereof can be obtained. The present invention provides a process for preparing a titanium oxide derivative using a sulfuric acid process, in which titanyl sulfate (TiOSO) produced by dissolving ilmenite in sulfuric acid4) Is subjected to hydrolysis and calcination to produce a titanium oxide derivative, wherein the hydrolysis includes the step of applying a pressure higher than the external atmospheric pressure.
Description
Technical Field
The present invention relates to a method for preparing a titanium oxide derivative, and more particularly, to a method for preparing a titanium oxide derivative such as nano-sized titanium dioxide through hydrolysis and calcination processes of a titanyl sulfate solution using a sulfuric acid process.
Background
Titanium dioxide nanoparticles are used not only as a raw material for white dyes and the like, but also as a raw material for various products such as chemical catalysts, catalysts used in electrochemical and photochemical industries, photocatalysts, gas sensors, photoconductors, solar cells, sunscreens, covering materials, and the like. For example, titanium dioxide has suitable bonding strength with oxygen and excellent acid resistance, and thus is used as a redox catalyst or a carrier. In addition, titanium dioxide has high UV-blocking properties, and thus is used as a raw material for cosmetics or as a plastic surface coating, and is also used for the preparation of antimicrobial agents, antifouling agents, hydrophilic coatings, and the like.
Titanium dioxide uses sulfur industriallyAcid process production, which comprises treating ilmenite as a feedstock with sulfuric acid or chlorine process production, which comprises treating a rutile mineral as a feedstock with chlorine or hydrogen chloride in the presence of a reducing agent (usually carbon). In the sulfuric acid process, ilmenite is dissolved in sulfuric acid, and after removing iron ions from the solution, drying and calcination are performed. The produced titanium dioxide mainly has an anatase crystal form, and sulfate ions and impurities remaining on the surface affect the titanium dioxide, and thus are known as factors that reduce the reactivity and quality of the finally produced product. In contrast, titanium tetrachloride (TiCl) in which the intermediate product is oxidized4) In the chlorine method for producing titanium dioxide, an almost uniform particle size distribution is obtained and also a trace amount of silicon (Si) and aluminum (Al) is contained, but the purity of titanium dioxide having a single structure is not known to be high (Bang Jin Jang, kyanggi University Department of Environmental Engineering, MS Thesis,2008, pp.60-62).
Various titanium dioxide crystal structures (crystal type or structure type) are known, such as anatase type, rutile type and brookite type titanium dioxide, and the use and properties of titanium dioxide vary greatly depending on the crystal habit, shape and size of particles. In particular, crystal shape and particle size are known to have significant effects on physicochemical, mechanical, electrical, magnetic and optical properties (x.chen, SSMao, j.noosci.nitotechnol., 2006, 6, 906-. For example, titanium dioxide in the anatase crystal form is reported to have the best photocatalytic activity and Selective Catalytic Reduction (SCR) reactivity, and is known to have a small and uniform particle size, a well-controlled aggregate state, and catalytic activity improved by an increased specific surface area (Bang Jin Jang, kyanggi University Department of Environmental Engineering, m.s. thesis,2008, pp.60-62).
However, it is known that it is not easy to prepare nanoparticles having a controlled size, distribution or specific surface area due to the rapid reactivity of the titanium dioxide precursor. Because of the rapid reactivity, titanium dioxide particles made using typical processes will form a granular form of aggregated crystals rather than a crystalline particulate form alone, and because of the granular form, will be indicated as having a particle size much larger than the actual particle size. Therefore, the particle size measured by x-ray diffraction (XRD) analysis, not the size of the prepared pellet, is generally given as the size of the nanoparticle. However, in many cases, the pellets do not readily disperse into individual particles, but rather exist as agglomerates or aggregates having strong affinity. In this case, the pellets have a smaller surface area than the actual individual nanoparticles can exhibit, and thus may exhibit poor performance when used in use situations requiring a large surface area that the titanium dioxide nanoparticles can inherently exhibit. Therefore, although methods including adding silica, alumina or an organic compound thereto to control the size and specific surface area of the titanium dioxide nanoparticles have been proposed, these methods basically involve the addition of impurities and thus may not be suitable depending on the use case. Further, although a method involving the use of additives such as an organic solvent such as alcohol and the like, a surface-substitution agent and a structure-directing agent, or a below-room-temperature cooling type production method and the like is known as a technique for controlling the uniformity of titanium dioxide particles (international patent publication WO 2011-.
Therefore, it is necessary to develop a technique in which an iron oxysulfate solution obtained by dissolving ilmenite in sulfuric acid in a typical titania process is typically used, and the size and surface area of titania nanoparticles are relatively easily controlled without adding other materials not derived from the titania production process, wherein titania nanoparticles having a desired size and surface area can be produced according to the use cases.
[ Prior art patent document ]
Korean patent No. 1441436 (9 month and 11 days 2014)
Chinese patent publication No. 103641164 (5 months and 19 days 2014)
Chinese patent publication No. 103073059(2013, 5 and 1)
International patent publication No. WO2013-147163 (10 months and 3 days in 2013)
Korean patent No. 1065804(2011 9 months and 9 days)
Korean patent No. 1042018(2011, 6 months and 9 days)
International patent publication No. WO2005-121026 (22/12/2005)
Korean patent No. 0430405 (4 month and 23 days 2004)
Korean patent No. 0374478 (19/2/2003)
Chinese patent publication No. 001541944 (11 months and 3 days in 2004)
Korean patent No. 0343395 (24/6/2002)
International patent publication No. WO2000-060130 (10 months and 12 days in 2000)
Korean patent No. 0224732(1999, 7 months and 15 days)
Korean patent publication No. 1997-0059094 (8/12/1997)
Korean patent No. 0077674 (9, 26, 1994)
-U.S. Pat. No. 5030439(1991, 7, 9)
Korean patent laid-open No. 1988-0003833 (30/3 in 1988)
Korean patent publication No. 0016154 (24/1/1984)
Korean patent laid-open No. 1983-0004159 (6.7.1983)
Disclosure of Invention
Technical problem
An object of the present invention is to provide a novel method for preparing a titanium oxide derivative using a sulfuric acid process, wherein the method allows the size or surface area of nanoparticle crystals or agglomerates to be adjusted by adjusting the pressure and temperature during hydrolysis and in the titanium oxide derivative crystallization or agglomerate formation and treatment step, to obtain a titanium oxide derivative such as metatitanic acid or titanium dioxide or the like, a hydrate thereof or physically and chemically formable nanoparticles thereof at a desired size and surface area.
Technical scheme
In order to overcome the above-mentioned limitations, there is provided a method for preparing a titanium oxide derivative, the method being characterized by using a sulfuric acid process in which hydrolysis and calcination are carried out by usingTitanyl sulfate (TiOSO) produced by dissolving ilmenite with sulfuric acid4) The titanium oxide derivative is prepared from a solution, wherein the hydrolysis comprises the step of applying a pressure higher than the external atmospheric pressure.
Further, there is provided a method for producing a titanium oxide derivative, characterized in that the step of applying pressure is performed under a pressure of 1.05 to 2 times atmospheric pressure based on the external atmospheric pressure.
Further, a method for producing a titanium oxide derivative is provided, which is characterized in that the step of applying pressure is performed at a temperature of 70 to 120 ℃.
In addition, a method for producing a titanium oxide derivative is provided, which is characterized in that the step of applying pressure is performed for 10 minutes to 4 hours.
Further, there is provided a process for producing a titanium oxide derivative, characterized in that the hydrolysis is carried out at a temperature of 70 to 120 ℃ under an external atmospheric pressure for 10 minutes to 4 hours before the step of applying pressure.
Further, there is provided a method for producing a titanium oxide derivative, characterized by repeating the steps of applying pressure and hydrolyzing under external atmospheric pressure, the hydrolysis being carried out for a total of 1 to 6 hours.
Further, there is provided a process for producing a titanium oxide derivative, characterized in that the hydrolysis is carried out at a temperature of 70 to 120 ℃ for 10 minutes to 4 hours under an external atmospheric pressure after the step of applying pressure.
Further, there is provided a method for producing a titanium oxide derivative, characterized by repeating the steps of hydrolysis and pressure application under external atmospheric pressure, the hydrolysis being performed for a total of 1 to 6 hours.
Further, a method for producing a titanium oxide derivative is provided, which is characterized in that calcination is carried out at 200-500 ℃ for 10 minutes to 3 hours.
Further, there is provided a method for producing a titanium oxide derivative, characterized in that the titanium oxide derivative is one or more selected from the group consisting of titanium oxide, titanium oxide salt, metatitanic acid, titanium oxide hydrate, and titanium dioxide.
Further, there is provided a process for producing a titanium oxide derivative, characterized in that the titanium oxide derivative is a titanium oxide derivative in which the single crystal particle diameter of the particles is 1 to 25 nm.
Further, there is provided a process for producing a titanium oxide derivative, characterized in that the titanium oxide derivative is one in which the specific surface area of the granular crystals is 70 to 200m2A titanium oxide derivative per gram.
Advantageous effects
In the method for producing a titanium oxide derivative using a sulfuric acid process, in order to produce a titanium oxide derivative having a desired particle diameter or particle size and specific surface area, such as metatitanic acid or titanium dioxide, etc., the F-value (amount of sulfuric acid/TiO) is adjusted by removing or adding iron ions in a titanyl sulfate solution by adjusting the addition amount of iron powder according to the composition of ilmenite, which is a raw material of a typical titanyl sulfate solution2Amount), Fe/TiO2Ratio and TiO2Amount/liter, etc. In a typical process for preparing a titanium oxide derivative using a sulfuric acid process, it is difficult to prepare a large amount of a titanium oxide derivative such as metatitanic acid or titanium oxide, etc. while controlling important factors determining the quality thereof, only by adjusting these variables and process conditions or temperature.
The present invention can provide a novel technique capable of adjusting a titanium oxide derivative, such as nanocrystalline metatitanic acid or titanium dioxide, having a desired particle diameter and surface area while forming the titanium oxide derivative in an extremely uniform state by controlling the particle size and specific surface area without even adjusting the variables as described above, by adjusting the point of time at which pressure is applied, the duration of the applied pressure, the temperature at which the pressure is applied, or the magnitude of the pressure applied during hydrolysis of the titanyl sulfate solution.
Further, by drying and polishing/crushing under optimum conditions the crystals of a titanium oxide derivative such as titanium dioxide or the like produced from a titanyl sulfate solution according to the present invention by hydrolysis under the application of a certain pressure, more uniform titanium oxide derivative particles can be produced.
Drawings
Fig. 1a to 1f are graphs showing XRD patterns of titanium dioxide nanoparticles prepared according to examples 2, 5, 8, 11, 13 and 14, respectively.
Fig. 1g and 1h are diagrams showing XRD reference patterns of anatase type titanium dioxide and rutile type titanium dioxide, respectively.
Fig. 2a to 2f are SEM images of the titanium dioxide nanoparticles respectively prepared according to examples 1 to 6 at a magnification of 50,000 times.
Fig. 3a to 3f are SEM images of the titanium dioxide nanoparticles respectively prepared according to examples 1 to 6 at a magnification of 200,000 times.
Fig. 4a to 4f are SEM images of the titanium dioxide nanoparticles respectively prepared according to examples 7 to 12 at a magnification of 50,000 times.
Fig. 5a to 5f are SEM images of the titanium dioxide nanoparticles respectively prepared according to examples 7 to 12 at a magnification of 200,000 times.
Fig. 6a and 6b are SEM images of titanium dioxide nanoparticles prepared according to examples 13 and 14, respectively, at 50,000 times magnification.
Fig. 7a and 7b are SEM images of the titanium dioxide nanoparticles respectively prepared according to examples 13 to 14 at a magnification of 200,000 times.
Detailed Description
Hereinafter, exemplary embodiments of the present invention will be described in detail. When it is determined that the detailed description about the related known art makes the essential features of the present invention unclear, the description is excluded. Throughout the specification, unless otherwise specifically stated, a portion "including" an element does not mean that other elements are excluded, but means that other elements may be further included.
The inventors have realized that the composition of ilmenite as a typical feedstock for titanyl sulfate solution can be manipulated to adjust variables such as F value (amount of sulfuric acid/TiO)2Amount), Fe/TiO2Ratio or no liter of TiO2After the amount and the like, in order to obtain a desired particle diameter or particle size and a desired specific surface area in a method for producing a titanium oxide derivative using a sulfuric acid process, a related study was conducted to adjust the average particle size and specific surface area of the titanium oxide derivative to desired values while having limitations in mass production of the titanium oxide derivativeAnd thus the present invention has been achieved after the unexpected results have been found, wherein by adjusting the point of time at which pressure is applied, the duration of the pressure application, the temperature at the time of the pressure application, or the magnitude of the applied pressure, etc., the titanium oxide derivative can be formed in an extremely uniform state while adjusting the particle diameter and the surface area to desired values, even without adjusting specific variables.
Accordingly, the present invention provides a process for producing a titanium oxide derivative, the process being characterized by using a sulfuric acid process in which titanyl sulfate (TiOSO) produced by dissolving ilmenite with sulfuric acid is hydrolyzed and calcined4) A titanium oxide derivative, wherein the hydrolysis includes a step of applying a pressure higher than an external atmospheric pressure. In order to more clearly understand the nature of the present invention before describing the present invention below, a titanium oxide production method using a typical sulfuric acid process will be described in examples.
First, ilmenite was dissolved in sulfuric acid by heating ilmenite and 93-96 wt% sulfuric acid of a raw material of titanium dioxide at 155-190 ℃. Here, 1-1.5 times the amount of sulfuric acid was used for 1 ton of ilmenite, and oxygen was blown in during dissolution to oxidize Fe (II) in ilmenite. The unoxidized Fe (II) and Ti (SO) produced as a result of the reaction as in reaction equation 14)2Becomes a solid material (solid phase material) existing in a crystalline form in a sulfuric acid solution.
[ equation 1]
2FeTiO3+5H2SO4→
TiOSO4+Ti(SO4)2+FeSO4+Fe+3+SO4 -2
Then, water was added in an amount of about 3 times the weight of the ilmenite to dissolve the solid matter, and the waste sulfuric acid obtained after hydrolysis as described below was added to adjust the concentration. The solid substance is dissolved while adding water, and thus the chemical reactions of the following reaction equations 2 and 3 occur.
[ equation 2]
Ti(SO4)2+H2O->TiOSO4+H2SO4
[ equation 3]
TiOSO4+2H2O->H2TiO3+H2SO4
Next, fe (iii) is reduced as in the following reaction equation 4 by adding iron powder to the solution obtained by the above reaction equations 2 and 3.
[ equation 4]
Fe (powder) +2Fe+3-＞3Fe+2
Fe (powder) +2Fe+3→3Fe+2
Subsequently, iron (II) sulfate and iron (II) sulfate heptahydrate (FeSO) are formed by vacuum depressurization4·7H2O) crystals, and iron (II) sulfate crystals and impurities are removed by reduced pressure and microfiltration.
Then, the titanyl sulfate solution is concentrated under reduced pressure while maintaining the temperature at 80 ℃ or less, and the concentrated titanyl sulfate solution is hydrolyzed at 95 to 105 ℃ for 3 to 8 hours to form metatitanic acid (TiO (OH)2) Crystals, as in equation 5.
[ equation 5]
TiOSO4+2H2O->TiO(OH)2+H2SO4
Subsequently, the metatitanic acid formed was filtered to remove sulfuric acid, and the metatitanic acid crystals were washed 2 to 3 times with distilled water, wherein a whitening agent was used as needed.
Next, the washed metatitanic acid crystals are washed and dried or calcined at high temperature according to the use case, and then subjected to crushing and polishing processes to complete the titanium dioxide product.
In this typical titanium dioxide production process using the sulfuric acid process, the F number, Fe/TiO, of the titanyl sulfate solution is adjusted prior to the hydrolysis unit process2Ratio and TiO per liter2In an amount to produce metatitanic acid crystals or titanium dioxide crystals by performing hydrolysis. At present, a catalyst having F value (amount of sulfuric acid/TiO) is used2Amount) of 1.75-1.85, Fe/TiO2TiO in a ratio of 0.26-0.28 per liter2The acid titanyl sulfate solution in an amount of 200-230g/L produces titanium dioxide or metatitanic acid. In addition, 0.3-0.45 Fe/TiO is used2The ratio produces titanium dioxide or metatitanic acid. However, it is extremely difficult to precisely and uniformly control the crystal size, which is one of the most important factors determining the quality of metatitanic acid or titanium dioxide.
Therefore, in a typical titania production method using a sulfuric acid method, metatitanic acid crystals or powder are produced by adjusting the composition of a titanyl sulfate solution and a separately added seed material for crystal formation, and in order to obtain metatitanic acid or titania crystals (or powder) or an agglomerate, it is necessary to adjust the composition of the titanyl sulfate solution and the reaction conditions of the titanyl sulfate solution. However, since there are process limitations such as adjustment regarding such variables, occurrence of additional changes due to differences in equipment environments or occurrence of costs due to process changes, the present inventors have made it possible to form titanium dioxide particles in a very uniform state by changing the pressure and temperature within a narrow range while performing the hydrolysis process and the heat treatment process after the hydrolysis process, without adjusting the variables, in order to overcome these limitations and as part of developing a more convenient technique.
Generally, if the pressure is increased during the crystallization process, a large amount of small metatitanic acid crystals may be rapidly formed. In the present invention, by employing a process in which pressure is applied in titanyl sulfate hydrolysis and by changing temperature conditions or the like while applying pressure, titanium dioxide particles having particle diameters and specific surface areas varying according to conditions can be produced, and by subsequently removing or recovering sulfuric acid by filtration, washing with water or distilled water and performing additional treatment as needed, and then calcining under optimum conditions, titanium dioxide particles in a very uniform state and adjusted to achieve desired particle diameters and surface areas can be formed.
In addition to titanium dioxide, the present invention can also be applied to a titanium oxide derivative that can be produced by a sulfuric acid process. That is, well-known titanium oxide derivatives can be obviously selected and prepared as titanium oxide derivatives. For example, the titanium oxide derivative may be titanium oxide, titanium oxide salt, metatitanic acid, titanium oxide hydrate, or the like.
The pressure applying step may be performed using a pressure of 1.05 to 2.0 times the external atmospheric pressure, more desirably 1.1 to 1.45 times the external atmospheric pressure, still more desirably 1.15 to 1.4 times the external atmospheric pressure. When the pressure application condition is more than 2 times greater than the external atmospheric pressure, the cost may increase, and the titanium oxide derivative particles may no longer be formed in a uniform state. Herein, "external atmospheric pressure" refers to the atmospheric pressure in the space in the reactor or the treatment apparatus in which the production of the titanium oxide derivative by the sulfuric acid process is carried out.
When the titanyl sulfate solution is hydrolyzed within the above-mentioned applied pressure range, the hydrolysis is desirably carried out under an elevated temperature condition to improve reactivity and conveniently control the particle diameter and specific surface area of the titanium oxide derivative produced. That is, the pressure applying step is desirably performed at a temperature of 70-120 ℃, and the hydrolysis may be performed for 10 minutes to 4 hours. Here, from the viewpoint of efficiency, the pressure applying step may be performed at a temperature of 80 to 110 ℃ for 10 minutes to 3 hours, and more desirably, may be performed at a temperature of 90 to 105 ℃ for 20 minutes to 2 hours.
In the present invention, the point of time at which the pressure application step is started is considered as a means for more conveniently adjusting the size and specific surface area of the produced titanium oxide derivative particles, and for further enhancing the 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 additional hydrolysis is performed at atmospheric pressure for a predetermined duration within a predetermined temperature range before or after the pressure application step. Specifically, the hydrolysis is performed under atmospheric pressure at a temperature of 70-120 ℃ for 10 minutes to 4 hours before or after the pressure applying step. Here, from the viewpoint of efficiency, the hydrolysis under atmospheric pressure may be more desirably performed at a temperature of 80 to 110 ℃ for 10 minutes to 3 hours, and more desirably at a temperature of 90 to 100 ℃ for 20 minutes to 2 hours. Here, even when the hydrolysis is started at the external atmospheric pressure and is performed while increasing the pressure to the above-described pressure application range, the same effect as the case where additional hydrolysis is performed at the external atmospheric pressure before or after the pressure application step can be exhibited.
Further, when the pressure application step and the hydrolysis process under the external atmospheric pressure are repeatedly performed, it is possible to prepare a titanium oxide derivative having a smaller particle diameter or particle size while slightly increasing the specific surface area of the finally prepared titanium oxide derivative. That is, in the present invention, the pressure application step and the hydrolysis under the external atmospheric pressure may be repeated, or the hydrolysis under the external atmospheric pressure and the pressure application step may be repeated. Herein, the hydrolysis is desirably carried out for a total of 1 to 6 hours, more desirably for a total of 2 to 5 hours, and more desirably for a total of 3 to 4 hours. Further, when repeated, the pressure applying step and the hydrolysis at the external atmospheric pressure may each be performed for 10 minutes to 3 hours, desirably 10 minutes to 2 hours, and more desirably 10 minutes to 1 hour or 10-30 minutes.
In the present invention, the calcination process finally produces titanium oxide derivative nanoparticles having desired particle size and specific surface area through temperature-raising treatment of titanium oxide crystals or agglomerates produced under pressure and temperature conditions. That is, in the present invention, desired particle size and specific surface area are achieved, wherein a target level for preparing a single crystal particle diameter of particles therein is 1 to 25nm, and the specific surface area of the crystal of the particles is 70 to 200m2Per g, it is desirable that the crystal has a particle diameter of 1.5 to 20nm and the specific surface area of the crystal particles is 80 to 170m2The calcination process may be performed at 200-500 ℃ for 10 minutes to 3 hours per gram of the titanium oxide derivative nanoparticles. Here, the calcination process may be performed at 250-450 ℃ for 1.5-2.5 hours to maximize the uniformity of the finally prepared titanium oxide derivative.
The titanium oxide derivative of the desired specification can be finally prepared by subjecting the titanium oxide derivative crystals or agglomerates obtained after the calcination process to crushing and polishing treatment.
Hereinafter, embodiments of the present invention will be described in detail so that the present invention can be implemented by those of ordinary skill in the art. However, the following examples are merely illustrative of the present invention, and the present invention is not limited to the embodiments described below.
Example 1
Heating and stirring titanyl sulfate solution (F value of 1.7-1.9, Fe/TiO 0.2-0.5)2Ratio, 120-170g of TiO per liter2An amount; in the following examples titanyl sulfate solutions with the same variables) were used while adding water or an aqueous sulfuric acid solution to dilute the solution to 170g of TiO per liter2The solution is heated (here, a small amount of seed crystals for stimulating crystallization may be added, but it is acceptable not to add seed crystals) to 95 ℃, then the temperature is set at 90 ℃, while hydrolysis is performed at 95 ℃ for 30 minutes at a typical atmospheric pressure, and then, after maintaining the pressure at 1.15 ± 0.1 times the atmospheric pressure for 1.5 hours and hydrolyzing again for 30 minutes at atmospheric pressure to form crystals (or crystals), filtration, washing, and necessary post-treatment are performed, calcination is performed at 270 ℃ for about 2 hours, and then crushing and polishing are performed to prepare titanium oxide nanoparticles.
Example 2
Titanium dioxide nanoparticles were prepared by the same method as example 1, except that the calcination temperature was adjusted to 350 ℃.
Example 3
Titanium dioxide nanoparticles were prepared by the same method as example 1, except that the calcination temperature was adjusted to 450 ℃.
Example 4
Titanium dioxide nanoparticles were produced by the same method as example 1, except that the temperature at the time of applying pressure was adjusted to 105 ℃.
Example 5
Titanium dioxide nanoparticles were produced by the same method as example 2, except that the temperature at the time of applying pressure was adjusted to 105 ℃.
Example 6
Titanium dioxide nanoparticles were prepared by the same method as example 3, except that the temperature at the time of applying pressure was adjusted to 105 ℃.
Example 7
Titanium dioxide nanoparticles were prepared by the same method as example 1, except that the applied pressure was adjusted to 1.40 ± 0.1 times atmospheric pressure.
Example 8
Titanium dioxide nanoparticles were prepared by the same method as example 2, except that the applied pressure was adjusted to 1.40 ± 0.1 times atmospheric pressure.
Example 9
Titanium dioxide nanoparticles were prepared by the same method as example 3, except that the applied pressure was adjusted to 1.40 ± 0.1 times atmospheric pressure.
Example 10
Titanium dioxide nanoparticles were prepared by the same method as example 4, except that the applied pressure was adjusted to 1.40 ± 0.1 times atmospheric pressure.
Example 11
Titanium dioxide nanoparticles were prepared by the same method as example 5, except that the applied pressure was adjusted to 1.40 ± 0.1 times atmospheric pressure.
Example 12
Titanium dioxide nanoparticles were prepared by the same method as example 6, except that the applied pressure was adjusted to 1.40 ± 0.1 times atmospheric pressure.
Example 13
The titanyl sulfate solution was heated while water or sulfuric acid solution was added to dilute the solution to 170g TiO per liter2Heating the solution (where a small amount of seed crystals for stimulating crystallization may be added, but it is acceptable not to add seed crystals) to 95 ℃, then setting the temperature of the solution to 105 ℃, while starting hydrolysis at 95 ℃ under normal atmospheric pressure, and performing hydrolysis (step 1) for 20 minutes while applying 1.15 ±.1After the pressure of 0.1 times atmospheric pressure was reduced to normal atmospheric pressure, hydrolysis (step 2) was carried out for 20 minutes. Next, after repeating the steps 1 and 2 to perform hydrolysis for a total of 160 minutes, filtration, washing and necessary treatment are performed, and then, calcination is performed at 350 ℃ for about 2 hours, followed by crushing and polishing to prepare titanium dioxide nanoparticles.
Example 14
Titanium dioxide nanoparticles were produced by the same method as example 13, except that the pressure applied in step 1 was adjusted to 1.40 ± 0.1 times atmospheric pressure.
Experimental example 1
Images (SU-70, FE-SEM, High Technologies) were captured using a Scanning Electron Microscope (SEM) to observe the overall shape of the titanium dioxide nanoparticles prepared according to the above examples, X-ray diffraction (XRD) analysis (PANalytical X' Pert X-ray diffractometer system) was performed to verify the structure type, particle size analysis was performed using a nanosizer Nano ZS90 to measure the particle size and size uniformity of the particles, and specific surface area (BET) was determined using a specific surface area analyzer (ASAP 2020, micietics).
Fig. 1a to 1f show XRD patterns of titanium dioxide nanoparticles prepared according to examples 2, 5, 8, 11, 13 and 14, respectively, and fig. 1g and 1h show XRD reference patterns of anatase type titanium dioxide and rutile type titanium dioxide, respectively. In addition, fig. 2a to 2f show SEM images of the titanium dioxide nanoparticles prepared according to examples 1 to 6 at 50,000 times magnification, respectively. Fig. 3a to 3f show SEM images of the titanium dioxide nanoparticles prepared according to examples 1 to 6 at a magnification of 200,000 times, respectively. Fig. 4a to 4f show SEM images of the titanium dioxide nanoparticles prepared according to examples 7 to 12 at 50,000 times magnification, respectively. Fig. 5a to 5f show SEM images of the titanium oxide nanoparticles prepared according to examples 7 to 12 at a magnification of 200,000 times, respectively. Fig. 6a and 6b show SEM images of the titanium dioxide nanoparticles prepared according to examples 13 and 14, respectively, at 50,000 times magnification, and fig. 7a and 7b show SEM images of the titanium dioxide nanoparticles prepared according to examples 13 and 14, respectively, at 200,000 times magnification. In addition, table 1 shows the single crystal particle size (XRD), specific surface area (BET), and aggregate particle size (d50) of the titanium dioxide nanoparticles prepared according to each example.
[ Table 1]
First, the titanium dioxide nanoparticles (examples 1 to 6) produced under the condition in which 1.5. + -. 0.1 times of external atmospheric pressure was applied exhibited mostly particle diameters in the range of 3.0 to 15.0nm, 80.0 to 170.0m2Specific surface area per gram (BET) and it can be seen that particles of relatively large particle size are formed at a pressing temperature of 90 ℃ (examples 1 to 3) versus a pressing temperature of 105 ℃ (examples 4 to 6). Further, the case where the temperature raising (calcination) treatment is performed after the hydrolysis, filtration and washing was examined, and it can be seen that the temperature raising treatment tends to form particles larger in particle size. Moreover, all the produced nanoparticles showed typical anatase XRD patterns (see fig. 1a and 1b), and the formation of irregularly shaped loosely packed agglomerates composed of uniform spherical particles not greater than 15nm was observed (see fig. 2 and 3).
Next, the titania nanoparticles produced under the pressure condition in which 1.40 ± 0.1 times of the external atmospheric pressure was applied (examples 7 to 12) exhibited shapes having the same tendency as those of the titania nanoparticles produced under the pressure condition in which 1.15 ± 0.1 times of the external atmospheric pressure was applied. Most exhibit a particle diameter in the range of 3.0 to 10.0nm and 90.0 to 170.0m2A specific surface area (BET) in the range of/g and forms particles of substantially similar particle size both at a temperature of 90 ℃ during hydrolysis (examples 7 to 9) and at a temperature of 105 ℃ during hydrolysis (examples 10 to 12). Examining the case where temperature rise (calcination) was performed after hydrolysis, filtration and washing, it can be seen that particles having a larger particle size were formed in the 450 ℃ treatment group (examples 9 and 12) than in the 270 ℃ treatment group (examples 7 and 10) or 350 ℃ treatment group (example 8 or 11). In addition, produceAll of the raw nanoparticles exhibited typical anatase XRD patterns (see fig. 1c and 1d) and the formation of irregularly shaped loosely packed agglomerates composed of uniform spherical particles no greater than 10nm was observed (see fig. 4 and 5).
Next, it was examined that the titanium oxide nanoparticles produced by repeating the pressurization step and the hydrolysis under the external atmospheric pressure (examples 13 and 14), the titanium oxide nanoparticles produced by applying a pressure of 1.15. + -. 0.1 times atmospheric pressure (example 13) had an average XRD particle diameter of 6.2nm, 173.10m2Specific surface area (BET) in g, agglomerate particle size (d) of 695nm50) And thus exhibit smaller particle size and particle size, and thus greater specific surface area than nanoparticles prepared under similar conditions but without repeated hydrolysis (example 5). In addition, the titanium dioxide nanoparticles (example 14) prepared by applying a pressure condition of 1.40. + -. 0.1 times atmospheric pressure had an average XRD particle diameter of 5.4nm, 167.60m2Specific surface area (BET) of/g, agglomerate particle diameter (d) of 783nm50) And thus confirmed to exhibit a specific surface area similar to that of the nanoparticle (example 11) prepared under similar conditions without repeating hydrolysis conditions, but with smaller particle size and particle size. Meanwhile, when conditions other than pressure are the same, the nanoparticles prepared under the condition in which 1.15 ± 0.1 times atmospheric pressure is applied (example 13) show a relatively larger particle size than the nanoparticles prepared under the condition in which 1.40 ± 0.1 times atmospheric pressure is applied (example 14). In addition, XRD analysis results of the prepared nanoparticles showed typical anatase structure (see fig. 1e and 1f), and it was observed in SEM images that the nanoparticles formed irregularly shaped loosely packed agglomerates composed of extremely small uniform spherical particles.
Above, exemplary embodiments of the present invention are described in detail. The description of the present invention is given to illustrate the present invention, and it will be understood by those skilled in the art to which the present invention pertains that the present invention can be easily modified into other specific forms without changing the technical concept or essential features thereof.
Therefore, the scope of the present invention is defined by the following claims, not the above detailed description, and all modifications or variations derived from the meaning and scope of the claims or their equivalent concepts should be construed as falling within the scope of the present invention.
Claims (7)
1. A process for producing a titanium oxide derivative, the process being characterized by using a sulfuric acid process in which TiOSO is produced by hydrolyzing and calcining TiOSO sulfate produced by dissolving ilmenite with sulfuric acid4A step of applying a pressure higher than an external atmospheric pressure, wherein hydrolysis is performed at a temperature of 70-120 ℃ for 10 minutes to 4 hours under the external atmospheric pressure before the step of applying the pressure, or hydrolysis is performed at a temperature of 70-120 ℃ for 10 minutes to 4 hours under the external atmospheric pressure after the step of applying the pressure,
wherein said steps of hydrolyzing at external atmospheric pressure and applying pressure are repeated with hydrolysis at external atmospheric pressure prior to said step of applying pressure, said hydrolysis being carried out for a total of 1-6 hours,
and in the case of hydrolysis at external atmospheric pressure after said step of applying pressure, repeating said step of applying pressure and hydrolysis at external atmospheric pressure, said hydrolysis being carried out for a total of 1-6 hours,
and in that said step of applying pressure is carried out at an atmospheric pressure of 1.05-2 times based on the external atmospheric pressure.
2. The method of claim 1, wherein said step of applying pressure is performed at a temperature of 70-120 ℃.
3. The method of claim 1, wherein the step of applying pressure is performed for 10 minutes to 4 hours.
4. The method as claimed in claim 1, wherein the calcination is carried out at 200-500 ℃ for 10 minutes to 3 hours.
5. The method according to any one of claims 1 to 4, characterized in that the titanium oxide derivative is one or more selected from the group consisting of titanium oxide, titanium oxide salt, metatitanic acid, titanium oxide hydrate, and titanium dioxide.
6. The method according to any one of claims 1 to 4, wherein the titanium oxide derivative is a derivative in which a single crystal particle diameter of particles is 1 to 25 nm.
7. The method according to any one of claims 1 to 4, wherein the titanium oxide derivative is one in which the specific surface area of the granular crystals is 70 to 200m2Derivatives per g.
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