Manganese-containing titanium oxide composite catalyst and odor removal method

Abstract

A composite catalyst according to one disclosure is a titanium oxide composite catalyst containing a transition metal including manganese, the composite catalyst containing one or more active oxygen species selected from the group consisting of surface-adsorbed oxygen and hydroxyl radicals on its surface, and having an absorbance (A 500 ) at 300 nm wavelength (A 300 ) divided by the ratio (A 500 / A 300 ) is 0.85 or more, and the hydrogen temperature-programmed reduction profile is characterized by a peak located in the temperature range of 240 to 275° C. The composite catalyst according to the present invention can effectively remove odors such as VOCs.

Description

[Technical Field]

[0001] The present invention relates to a manganese-containing titanium oxide composite catalyst and a method for removing odors using the same. [Background technology]

[0002] Various odors coming in from the external environment are considered a serious social problem and are the cause of various petitions, so effective treatment methods suitable for each environment are required. On the other hand, odors in enclosed spaces such as residential spaces such as homes, hotels, and restaurants, and means of transportation such as automobiles and subways cause discomfort and can transfer to residents and various items in enclosed spaces where odors are generated, so technology is required to steadily remove odors to below an appropriate concentration.

[0003] Chemical odor removal equipment has safety issues, making it difficult to install, especially in closed spaces, so odors are removed using adsorbents. However, adsorbents have a limited adsorption capacity and require regeneration or periodic replacement. However, it is difficult for consumers to regenerate adsorbents, and they have the disadvantage of needing to be replaced periodically. Furthermore, in closed environments where the amount of odor emission is not constant, the lifespan of adsorbents is also not constant, and odors are easily transferred to other items in the vicinity, resulting in troublesome use.

[0004] While catalytic odor removal technology has the advantage of not requiring periodic replacement, it suffers from the drawback of a short catalyst lifespan due to a rapid decline in catalytic activity in low-temperature or humid environments. Therefore, there is a need for the development of oxidation catalysts that can maintain a constant catalytic activity even under a variety of harsh conditions, are highly reliable over a long period of time, and have the ability to remove odors. Summary of the Invention [Problem to be solved by the invention]

[0005] The main problem to be solved by the present invention is to provide a catalyst having excellent activity that can remove odorous and harmful gases under severe conditions such as a humid environment.

[0006] Another aspect of the present invention is to provide a long-life oxidation catalyst that can remove odors over a long period of time without further regeneration steps in a closed environment.

[0007] Another object of the present invention is to provide a highly active oxidation catalyst capable of oxidizing a variety of odors including various volatile organic compounds at a relatively low temperature. [Means for solving the problem]

[0008] The composite catalyst according to one embodiment is a titanium oxide composite catalyst containing a transition metal including manganese, and the composite catalyst contains, on its surface, one or more active oxygen species selected from the group consisting of surface-adsorbed oxygen and hydroxyl radicals, and has an absorbance (A 500 ) at 300 nm wavelength (A 300 ) divided by the ratio (A 500 / A 300 ) is 0.85 or more, and a peak is located in the temperature range of 240 to 275°C in the hydrogen temperature-programmed reduction profile.

[0009] In one embodiment, a second peak may be located in a temperature range of 345 to 420°C in the hydrogen temperature-programmed reduction profile of the composite catalyst.

[0010] In one specific example, the X-ray photoelectron spectroscopy (XPS) spectrum of the composite catalyst has a lattice oxygen peak derived from lattice oxygen, an adsorbed oxygen peak derived from surface-adsorbed oxygen, and a hydroxyl peak derived from hydroxyl radicals, and the ratio ([O2+O3] / O1×100,%) obtained by dividing the sum of the area of ​​the hydroxyl peak (O3) and the area of ​​the adsorbed oxygen peak (O2) by the area of ​​the lattice oxygen peak (O1) is 45 to 85%, and the ratio (O3 / O2×100,%) obtained by dividing the area of ​​the hydroxyl peak (O3) by the area of ​​the adsorbed oxygen peak (O2) is 50% or less.

[0011] In one embodiment, in the oxygen thermal desorption profile of the composite catalyst, a first area fraction (A ) is a first area fraction (A ) of the area integrated under the oxygen thermal desorption profile in the temperature range of 500-600°C relative to the total area integrated under the oxygen thermal desorption profile in the temperature range of 40-850°C. 500-600 ) is 1-20%, and the second area fraction (A 600-850 ) can be 20 to 40%.

[0012] In one embodiment, in the X-ray diffraction pattern of the composite catalyst, the intensity of the diffraction peak of the (101) plane of the anatase phase is I 101 is the intensity of the diffraction peak of the (110) plane of the rutile phase. 110 Intensity ratio (I 101 / I 110 ) can be 4 to 8.

[0013] In one embodiment, in the X-ray diffraction pattern of the composite catalyst, the intensity of the diffraction peak of the (101) plane of the anatase phase is I 101 The diffraction peak intensity of the (200) plane of the anatase phase is I 200 Intensity ratio (I 101 / I 200 ) can be 4.15 or less.

[0014] In one embodiment, the X-ray diffraction pattern may be free of diffraction peaks due to manganese and manganese oxides.

[0015] In one embodiment, the manganese may be contained in an amount of 1 to 15 wt % based on the total weight of the composite catalyst.

[0016] In one embodiment, the transition metal can comprise manganese.

[0017] In one embodiment, the composite catalyst can be a catalyst for decomposing volatile organic compounds.

[0018] The present invention includes an odor gas removing agent containing the above composite catalyst.

[0019] The present invention includes a method for removing odorous gases using the composite catalyst described above.

[0020] A method for removing odorous gases according to one embodiment includes the steps of: S1) supplying a first gas containing an odorous gas to a reaction space in which a titanium oxide composite catalyst containing a transition metal including manganese is located; S2) bringing the odorous gas in the first gas into contact with the composite catalyst to decompose the odorous gas; and S3) discharging a second gas produced by decomposition of the odorous gas from the reaction space.

[0021] In one embodiment, the odorous gas may include any one selected from the group consisting of aldehyde-based compounds, aromatic hydrocarbons, aliphatic hydrocarbons, ammonia-based compounds, and mercaptan-based compounds.

[0022] In one embodiment, in the step S1), the first gas may contain moisture. [Effects of the Invention]

[0023] The catalyst according to one embodiment can effectively remove harmful gases, including odors, under harsh conditions such as humid environments.

[0024] According to another embodiment, the catalyst can maintain constant catalytic activity in a low-temperature or humid environment, and can eliminate odors for a long period of time without requiring a further regeneration step in a closed environment. Specifically, the catalyst according to the present invention can eliminate various odors, including mercaptan compounds, in a low-temperature and high-humidity refrigerated environment, and provides high convenience because a further regeneration step due to catalyst poisoning is not required.

[0025] Another embodiment of the catalyst can effectively oxidize a variety of odor-causing volatile organic compounds at relatively low temperatures.

[0026] Another embodiment of the catalyst can effectively remove odorous gases reliably over an extended period of time. [Brief explanation of the drawings]

[0027] [Figure 1] 1 is a transmission electron microscope photograph (scale bar 50 nm) of the titanium oxide used as a raw material in the examples and the composite catalyst 1 produced in Example 1. [Figure 2] 1 is a diagram showing the results of UV-Vis spectroscopy of composite catalyst 1 produced in Example 1. FIG. [Figure 3] FIG. 10 is a diagram showing the results of UV-Vis spectroscopy of composite catalyst 7 produced in Example 7. [Figure 4] FIG. 1 shows the results of UV-Vis spectroscopy of Comparative Catalyst 4 produced in Comparative Example 4. [Figure 5] FIG. 1 shows the H2-TPR profile of composite catalyst 1 prepared in Example 1. [Figure 6] FIG. 1 shows the O 1s XPS spectrum of composite catalyst 1 prepared in Example 1. [Figure 7] 1 is an O2-TPD profile of composite catalyst 1 prepared in Example 1. [Figure 8] 1 is an X-ray diffraction pattern of composite catalyst 1 prepared in Example 1. [Figure 9]1 shows an X-ray diffraction pattern of Comparative Catalyst 4 prepared in Comparative Example 4. DETAILED DESCRIPTION OF THE INVENTION

[0028] Unless otherwise defined, technical and scientific terms used in this specification have the meanings that are commonly understood by those having ordinary knowledge in the technical field to which this invention belongs, and in the following description and accompanying drawings, descriptions of known functions and configurations that may obscure the gist of the present invention will be omitted.

[0029] Also, as used herein, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0030] Furthermore, units used in this specification unless otherwise specified are based on weight, and for example, the units of % or ratio mean % by weight or weight ratio, and unless otherwise defined, % by weight means the weight % of any one component of the total composition.

[0031] In addition, the numerical ranges used herein include the lower and upper limits, all values ​​within the range, increments logically derived from the form and width of the defined range, all doubly limited values, and all possible combinations of upper and lower limits of numerical ranges limited in different forms. Unless otherwise specified in the specification of the present invention, values ​​outside the numerical range that may occur due to experimental error or rounding off of values ​​are also included in the defined numerical range.

[0032] As used herein, the term "comprising" is an open-ended term having the same meaning as terms such as "comprising," "containing," "having," or "characterized by," and does not exclude further unrecited elements, materials, or steps.

[0033] In this specification, when a part such as a film (layer), region, or component is said to be on top of another part, this includes not only the case where it is directly on top of and in contact with the other part, but also the case where another film (layer), other region, other component, etc. is interposed between them.

[0034] In this specification, the term "pollutant" refers to any substance known to cause odor or pollute the air, soil, or water, but more advantageous effects can be achieved with odor-causing air pollutants. Specifically, the pollutant may be a volatile organic compound (VOC). The VOC may be an aldehyde-based compound, an aromatic hydrocarbon-based compound, an aliphatic hydrocarbon-based compound, an ammonia-based compound, or a mercaptan-based compound. Specific examples of the VOC include, but are not limited to, methane, ethylene, formaldehyde, acetaldehyde, toluene, benzene, xylene, ethylene, styrene, ethylbenzene, acetaldehyde, trimethylamine, and methyl mercaptan.

[0035] In this specification, titanium oxide refers to titanium dioxide, which can be expressed by the chemical formula TiO2, but does not necessarily refer to a material in which Ti and O have a mathematically strict integer ratio of 1:2. As is well known, the ratio of Ti and O may deviate to some extent from 1:2 due to the inclusion of unavoidable impurities, doping with metal elements, unavoidable defects, and / or adsorbed oxygen species or radicals. As a non-limiting example, titanium oxide is TiO 2-x where x can be 0 to 0.5, 0 to 0.4, 0 to 0.3, 0 to 0.2, or 0 to 0.1.

[0036] <Composite catalyst> The composite catalyst according to one embodiment relates to a titanium oxide composite catalyst containing a transition metal including manganese, and the composite catalyst contains, on its surface, one or more active oxygen species selected from the group consisting of surface-adsorbed oxygen and hydroxyl radicals, and has an absorbance (A) at a wavelength of 500 nm in a UV-Vis spectroscopy spectrum. 500 ) at 300 nm wavelength (A 300 ) divided by the ratio (A 500 / A 300 ) is 0.85 or more, and a peak is located in the temperature range of 240 to 275°C in the hydrogen temperature-programmed reduction profile.

[0037] UV-Vis spectrum A 500 / A 300 When the value satisfies 0.85 or more and the peak is located in the temperature range of 240 to 275°C in the hydrogen temperature-programmed reduction profile, the composite catalyst can have both high activity and moisture resistance.

[0038] Advantageously, in the UV-Vis spectroscopy spectrum, A 500 / A 300 The value can be 0.87 or more, 0.89 or more, 0.90 or more, 0.91 or more, 0.92 or more, or 0.93 or more, and can be substantially 1.00 or less or 0.98 or less. 500 / A 300 The value can be 0.90 to 0.98, 0.92 to 0.98, or 0.93 to 0.98. More advantageously, the composite catalyst has the aforementioned A 500 / A 300 The absorbance (A) at 700 nm in the UV-Vis spectrum is 700 ) at 300 nm wavelength (A 300 ) divided by the ratio (A 700 / A 300 ) can be 0.85 to 0.97, specifically 0.87 to 0.95.

[0039] The magnitude and position of the peak in the H-Temperature Programmed Reduction (H-TPR) profile may be physical properties determined by the oxidation value of the manganese (manganese ion) contained in the composite catalyst, the activity level of the manganese (manganese ion) having a specific oxidation value, and the content level of the manganese (manganese ion) having a specific oxidation value.

[0040] In addition to the UV-Vis spectrum, the H2-TPR profile of the composite catalyst shows a peak in the low temperature range of 240-275°C, which indicates that the composite catalyst has high activity for removing pollutants, especially mercaptan compounds, and also has improved moisture resistance.

[0041] Advantageously, the peak in the H2-TPR profile of the composite catalyst can be located in the temperature range of 245-275°C, more advantageously in the temperature range of 250-275°C, in which case the composite catalyst can have improved moisture resistance along with high activity.

[0042] In the H2-TPR profile of the composite catalyst, the peak located in the temperature range of 240 to 275°C is designated as the first peak, and the composite catalyst may have a second peak located in the temperature range of 345 to 420°C in the H2-TPR profile. The first peak may be due to manganese (manganese ion) with a higher oxidation value, and the second peak may be due to manganese (manganese ion) with a lower oxidation value. In the H2-TPR profile, the second peak may be located in the temperature range of 345 to 420°C, preferably 345 to 380°C, and more preferably 350 to 380°C, thereby enabling the composite catalyst to have high activity and long-term moisture resistance.

[0043] While not necessarily limited to this interpretation, it can be interpreted that in order to ensure both high activity and long-term moisture stability, manganese doped at lattice sites, defect sites, interstitial sites, etc. in titanium oxide has instability that allows it to effectively act as an active site or causes instability in the structure of the surrounding titanium oxide, and when excessive instability is suppressed, both activity for contaminant removal and long-term moisture stability are ensured. The degree of instability possessed by or caused by manganese can be represented by the temperature of the first peak in the H2-TPR profile, the temperature between the first peak and the second peak, the temperature between the first peak and the second peak, and the ratio (H1 / H2) of the height of the first peak (H1) to the height of the second peak (H2).

[0044] In one advantageous example, the above-mentioned first peak temperature and second peak temperature are satisfied, and the ratio (H1 / H2) of the height of the first peak (H1) to the height of the second peak (H2) in the H2-TPR profile is 0.5 or more, specifically 0.5 to 5.0, and preferably H1 / H2 is 2.0 to 5.0. In the above-mentioned H2-TPR profile, the position of a peak refers to the position of the highest point of the peak, and the position of a peak in a certain temperature range may mean that the temperature at the highest point of the peak falls within the temperature range.

[0045] In an X-ray photoelectron spectroscopy (XPS) spectrum, the composite catalyst has a lattice oxygen peak derived from lattice oxygen, an adsorbed oxygen peak derived from surface-adsorbed oxygen, and a hydroxyl peak derived from hydroxyl radicals, and a first area ratio ([O2+O3] / O1×100,%) obtained by dividing the sum of the area of ​​the hydroxyl peak (O3) and the area of ​​the adsorbed oxygen peak (O2) by the area of ​​the lattice oxygen peak (O1) is 45 to 85%, and a second area ratio (O3 / O2×100,%) obtained by dividing the area of ​​the hydroxyl peak (O3) by the area of ​​the adsorbed oxygen peak (O2) can be 50% or less, specifically 10 to 50%.

[0046] When the composite catalyst satisfies the first area ratio of 45 to 85% and the second area ratio of 50% or less in the XPS O 1s spectrum, specifically the second area ratio of 5 to 50%, the composite catalyst can exhibit high oxidation activity against a variety of odor-inducing VOCs in pollutants, such as aldehyde compounds, aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, ammonia compounds, or mercaptan compounds.

[0047] Although not necessarily limited to this interpretation, the first area ratio and the second area ratio in the XPS O 1s spectrum represent the oxidation ability (activity as an oxidation catalyst) of the composite catalyst against pollutants, specifically VOCs that cause odor, and can be interpreted as meaning that the composite catalyst has a large amount of surface-adsorbed oxygen and hydroxyl radicals, and that the surface-adsorbed oxygen is more advantageous than the hydroxyl radicals in improving the oxidation ability against various VOCs.

[0048] In an advantageous example, while satisfying the above-mentioned UV-Vis spectral properties and H2-TPR profile characteristics, the first area ratio may be 60 to 80%, and the second area ratio may be 10 to 30%.

[0049] The composite catalyst can satisfy the aforementioned UV-Vis spectral properties and H2-TPR profile characteristics, as well as the aforementioned XPS O 1s spectral properties. A composite catalyst with these properties exhibits high oxidation activity for various VOCs, excellent moisture resistance, and improved oxidation activity even at low temperatures in the presence of large amounts of moisture.

[0050] The composite catalyst exhibited a first area fraction (A ) of the total area integrated under the O 2 -Temperature Programmed Desorption (O 2 -TPD) profile measured in the temperature range of 40-850 °C, which is the area integrated under the O 2 -TPD profile in the temperature range of 500-600 °C. 500-600 ) can be 1 to 20%, specifically 10 to 20%, and the second area fraction (A 600-850 ) can be 20 to 40%, specifically 20 to 30%.

[0051] Although not necessarily limited to this interpretation, the temperature ranges of 500 to 600°C and 600 to 850°C in the O2-TPD profile can be interpreted as indicating the instability of lattice oxygen including the surface-adjacent region of the composite catalyst, in other words, the crystallographic stability in the internal region of the composite catalyst including the surface-adjacent region.

[0052] When the composite catalyst has relatively low values ​​of the first area fraction and the second area fraction, the composite catalyst can maintain stable crystallinity, including the surface-adjacent region, despite its high activity, and have improved durability.

[0053] The composite catalyst can satisfy the above-mentioned UV-Vis spectroscopic properties and H2-TPR profile characteristics, as well as the above-mentioned O2-TPD properties. A composite catalyst satisfying these properties can exhibit high activity, improved moisture resistance, and improved durability. This improved durability allows excellent catalytic activity to be stably maintained over a wide temperature range for a long period of time.

[0054] The composite catalyst may contain titanium dioxide in the crystallographic anatase phase, and preferably in both the anatase and rutile phases. The anatase and rutile crystalline phases can be confirmed by X-ray diffraction analysis. The presence of one or more diffraction peaks corresponding to the diffraction peak positions of titanium dioxide in the anatase phase and titanium dioxide in the rutile phase as defined by the JCPDS can define the composite catalyst as containing the anatase and rutile crystalline phases. The crystal size of the composite catalyst based on the X-ray diffraction pattern can be on the order of 10 to 40 nm, but is not limited thereto.

[0055] The relative content of anatase and rutile phases in the composite catalyst can be determined by the maximum intensity of the diffraction peak of the (101) plane of the anatase phase in the X-ray diffraction pattern. 101 and the maximum intensity I of the diffraction peak (2θ 27.7°) of the (110) plane of the rutile phase. 110 Intensity ratio I 101 / I110 In one advantageous example, I 101 / I 110 The r is preferably 4 to 8, more preferably 5 to 7, and even more preferably 6 to 7. Titanium oxide having such a mixed phase of anatase and rutile phases is advantageous in that it can further improve catalytic activity due to the synergistic effect of the two phases. However, it should not be construed that the titanium oxide contained in the composite catalyst of the present invention is composed of anatase and rutile phases. The composite catalyst may further contain titanium oxide having a brookite phase and / or an amorphous phase.

[0056] X-ray diffraction patterns can reveal the macroscopic properties of the crystallinity of composite catalysts. The degree of crystallographic deformation / distortion caused by doping with transition metals, including manganese, and the titanium oxide, which is the matrix doped in the composite catalyst, maintains stable crystallinity, can be determined by the maximum intensity I of the diffraction peak (2θ 25.3°) of the (101) plane of the anatase phase in the X-ray diffraction pattern of the composite catalyst. 101 is the maximum intensity of the diffraction peak of the (200) plane of the anatase phase. 200 Intensity ratio (I 101 / I 200 ) can be predicted by. 101 / I 200 can be 4.15 or less, specifically 2.50 to 4.15, and more specifically 2.50 to 4.10.

[0057] The composite catalyst may contain manganese (Mn), or may further contain, together with manganese (Mn), one or more metals selected from the group consisting of iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn). In one advantageous example, the composite catalyst may include titanium oxide doped with a transition metal, including manganese. In one practical example, the composite catalyst may be a composite catalyst containing manganese-doped titanium oxide, or a composite catalyst containing manganese and titanium oxide co-doped with one or more metals selected from the group consisting of iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn).

[0058] The composite catalyst may have a particulate shape, and the average particle size of the particles is D 50 The average particle size can be defined as the volume-based median diameter (D 50 ) can mean the volumetric basis D 50 means the particle size at the point where the cumulative volume percentage is 50% on the distribution curve (cumulative distribution curve) accumulated in order of particle diameter. 50 The cumulative distribution curve including the above can be obtained by a conventional particle size analyzer using a laser diffraction method or a dynamic light scattering method.

[0059] D of particulate composite catalyst 50 The value can be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, 0.7 μm or more, 0.8 μm or more, or 1 μm or more, and can be 1000 μm or less, 800 μm or less, 700 μm or less, 500 μm or less, 100 μm or less, 50 μm or less, 1 μm or less, 0.5 μm or less, or 0.1 μm or less. For example, it can be 0.01 μm to 1000 μm, 0.05 μm to 0.5 μm, 1 μm to 500 μm, 0.01 μm to 0.1 μm, or 0.01 μm to 1 μm.

[0060] The BET specific surface area of ​​the composite catalyst is 40-60m 2 / g, specifically 40-55m 2 / g, more specifically 40-50m 2 / g.

[0061] Based on the total weight of the composite catalyst, the content of manganese contained in the composite catalyst may be 1 to 15 wt %, specifically 3 to 13 wt %, and more specifically 4 to 9 wt %.

[0062] The composite catalyst according to an embodiment can be effective in decomposing or removing pollutants. One example of the decomposition or removal of pollutants can be the oxidation of pollutants, which means that the composite catalyst according to an embodiment is used to convert pollutants into other environmentally safe chemical species through catalytic oxidation reactions.

[0063] The composite catalyst can decompose pollutants at low, medium, and high temperatures, specifically, at a low temperature range of -20 to 10°C, a medium temperature range of 10 to 100°C, and a high temperature range of 100 to 300°C.

[0064] The composite catalyst according to one embodiment has excellent long-term activity, maintaining catalytic activity relatively constant even in low-temperature and humid environments and eliminating the need for additional steps for catalyst regeneration. Because the composite catalyst has excellent long-term activity, it can continuously oxidize and remove pollutants even in a closed environment where pollutants are continuously generated. Therefore, simply by installing the composite catalyst in a certain space in the closed environment, contamination of the closed environment by pollutants can be effectively prevented.

[0065] <Method of manufacturing composite catalyst> One aspect of the present invention relates to a method for producing a titanium oxide composite catalyst containing a transition metal including manganese, and relates to the method for producing the composite catalyst of the above-mentioned embodiment. Therefore, the method for producing the composite catalyst includes all of the above-mentioned features of the composite catalyst.

[0066] A method for producing a composite catalyst according to one embodiment includes the steps of: 1) preparing a dispersion in which titanium oxide particles are dispersed; 2) preparing a precursor solution in which a transition metal precursor including a manganese precursor is dissolved; 3) mixing the dispersion with the precursor solution to prepare a mixture; 4) adjusting the pH of the mixture to a strong basic range of 10.5 to 12.5; 5) vacuum-filtering the mixture whose pH has been adjusted to a strong basic range to recover a solid; and 6) drying the recovered solid and calcining it at a temperature of 250 to 400°C for 2 to 4 hours.

[0067] Step 1) is a step of dispersing titanium oxide particles in a solvent to prepare a dispersion, and step 2) is a step of dissolving transition metal precursors, including a manganese precursor, in a solvent to prepare a precursor solution. The solvents for steps 1) and 2) can be, independently of each other, polar solvents, specifically polar protic solvents. For example, the solvents for steps 1) and 2) can be, independently of each other, a (C1-C7) alcohol, water, or a co-solvent thereof, specifically a (C1-C4) alcohol, water (including deionized water), or a co-solvent thereof, more specifically water.

[0068] The titanium oxide particles of stage 1 can advantageously be particulate titanium oxide having a mixture of anatase and rutile phases. 50 The thickness may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, 0.7 μm or more, 0.8 μm or more, or 1 μm or more, and may be 1000 μm or less, 800 μm or less, 700 μm or less, 500 μm or less, 100 μm or less, 50 μm or less, 1 μm or less, 0.5 μm or less, or 0.1 μm or less. For example, the thickness may be 0.01 μm to 1000 μm, 0.05 μm to 0.5 μm, 1 μm to 500 μm, 0.01 μm to 0.1 μm, or 0.01 μm to 1 μm, but is not limited thereto. The titanium oxide particles may be a commercial product in which anatase phase and rutile phase are mixed, and a representative example of such a commercial product is P25 (Evonik).

[0069] The transition metal precursor, including the manganese precursor of step 2, can be any transition metal compound that can be dissolved in a polar solvent, specifically, a polar protic solvent. For example, the precursor can be one or a combination of two or more selected from the group consisting of manganese acetate (Mn(Ac)), manganese nitrate (Mn(NO)), manganese chloride (MnCl), manganese acetylacetonate (Mn(acac)), and hydrates thereof. Preferably, the manganese precursor can be one or more selected from the group consisting of manganese acetate and manganese acetylacetonate, which are organic-based precursors.

[0070] The dispersion liquid in step 1) may contain titanium oxide particles in an amount of 0.1 to 5 wt %, specifically 0.5 to 4 wt %, and the precursor solution in step 2) may contain a transition metal precursor in an amount of 0.1 to 5 wt %, specifically 0.3 to 3 wt %, but is not necessarily limited thereto.

[0071] The transition metal precursor including the manganese precursor may be dissolved in a solvent and mixed with the titanium oxide dispersed in the solvent. The dispersion and the precursor solution in step 3 may be mixed so that the transition metal is in a range of 1 to 15 wt %, preferably 1 to 10 wt %, more preferably 4 to 9 wt %, based on the total weight of the titanium oxide and the transition metal, taking into account the mass of the titanium oxide and the mass of the transition metal including the manganese contained in the precursor solution.

[0072] In step 4), the mixed solution may be adjusted to a pH of 11.0 to 12.5, preferably 11.0 to 12.0, in the strongly basic range, using a pH adjuster. The pH adjuster may be dissolved in a polar protic solvent, such as water, and added to the mixed solution. The pH adjuster may be a base such as ammonia, an amine compound, a quaternary ammonium compound, an alkali metal hydroxide, or an alkaline earth metal hydroxide, preferably an alkali metal hydroxide, more preferably NaOH or KOH, and even more preferably NaOH. The mixed solution whose pH has been adjusted to a strongly basic range may be stirred for 10 to 60 minutes, specifically 20 to 50 minutes, but is not limited thereto.

[0073] Step 5) is a step of separating and recovering solids from the reaction mixture. To separate and recover solids, any separation means known in the art, such as filtration or centrifugation, may be selected without limitation.

[0074] The recovered solid is dried and calcined in step 6) to produce a manganese-containing composite catalyst. The drying in step 6) may be performed at a temperature of 100 to 200°C, specifically 100 to 150°C. The drying time may be 2 to 24 hours, but is not limited thereto. The calcination in step 6) may be performed at a temperature of 250 to 400°C, preferably 300 to 350°C, for 2 to 4 hours. The calcination of the dried solid may be performed in air, and the temperature rise rate during drying or calcination may be 1 to 10°C / min, but is not necessarily limited thereto.

[0075] The solid matter recovered from the mixed solution may be washed with water before drying, or may be dried in an unwashed state, and preferably may be dried in a state recovered by solid-liquid separation such as filtration without being washed.

[0076] <Odor gas remover> Yet another aspect of the present invention relates to an odor gas remover comprising a titanium oxide composite catalyst containing a transition metal including manganese. The odor gas remover may comprise the composite catalyst of the above-described embodiment. Thus, the odor gas remover includes all of the above-described features of the composite catalyst.

[0077] In one embodiment, the odor gas remover may be a composite catalyst. The odor gas remover may include composite catalyst particles (powder), an agglomerate of particulate composite catalysts, or a molded product of a composite catalyst molded into a desired shape. In this case, the shape of the molded product of the composite catalyst may be any shape commonly used in the field of removing odor gases using catalysts. Substantial examples of the molded product include, but are not limited to, a bulk shape, a spherical particle shape, a cylindrical or ring-shaped pellet shape, a honeycomb shape, a fiber shape, and the like.

[0078] In one embodiment, the odor gas remover may be a coated product in which the composite catalyst is coated on a support. The support may be a ceramic support such as alumina, silicon nitride, silica, zeolite, etc.; a metal support such as stainless steel; a carbon-based support such as activated carbon; or an organic support such as a synthetic resin, a natural polymer, a biocompatible polymer, a thermosetting resin, a thermoplastic resin, or a mixture thereof. The shape of the support is not particularly limited, but may be a honeycomb, a sphere, a cylindrical or ring-shaped pellet, a plate, a porous mesh or porous foam, or a woven or non-woven fiber. As a more practical example, the odor gas remover may include a fabric, a filter, a film, or a fiber having the composite catalyst incorporated therein or on its surface. In this case, the filter may be a gas treatment filter, and the gas may be air (atmospheric atmosphere).

[0079] The odor gas remover can be prepared by a method commonly used for coating a catalyst material on a support, such as dipping, spraying, slurry coating, etc. The odor gas remover can contain 5 to 50 wt % of the composite catalyst based on the total weight of the support and the composite catalyst, but is not limited thereto. In this case, it goes without saying that a binder component can be used, if necessary, to stably fix the composite catalyst to the support.

[0080] <Articles with odorous gas removal capabilities> Yet another aspect of the present invention relates to an article comprising a titanium oxide composite catalyst containing a transition metal including manganese. The article having the ability to remove odorous gases by the composite catalyst can comprise the composite catalyst of the above-mentioned embodiment. Therefore, the article includes all of the above-mentioned features of the composite catalyst.

[0081] The article having odorous gas removing ability can be an article that is required to have odorous gas removing properties and that contains the composite catalyst or the odorous gas removing agent on the surface of the article or in a predetermined space of the article. When the composite catalyst is contained on the surface, examples include an article body having a surface region formed by the composite catalyst, and an article body having a coating layer containing the composite catalyst formed on any surface thereof.

[0082] A substantial example of an article having odor gas removal capability is a storage device equipped with a composite catalyst or the above-mentioned odor gas remover, in which food, medicines, industrial goods, etc. are stored, and a more substantial example is a refrigerated storage device.

[0083] <Method for removing odorous gas> One aspect of the present invention relates to a method for removing odorous gases, comprising the steps of: S1) supplying a first gas containing an odorous gas to a reaction space in which a titanium oxide composite catalyst containing a transition metal including manganese is located; S2) bringing the odorous gas in the first gas into contact with the composite catalyst to decompose the odorous gas; and S3) discharging a second gas generated by decomposition of the odorous gas from the reaction space, wherein the composite catalyst is the composite catalyst of any of the above-described embodiments. Thus, the method for removing odorous gases includes all of the above-described features of the composite catalyst.

[0084] The composite catalyst in the reaction space can be a fluidized bed or a fixed bed, and as a practical example, a predetermined region of the reaction space can be filled with the composite catalyst or a composite catalyst having the form of the odor gas removal agent described above.

[0085] The first gas can be air (atmosphere) containing an odorous gas, but is not necessarily limited to this.

[0086] The reaction space may be an open space into which the first gas flows and from which the second gas can be discharged. The open space may be realized by an opening that separates the reaction space and connects the inside and outside of the reactor, but is not necessarily limited thereto. A composite catalyst is located inside the reactor, and the first gas may flow into the reactor. Odorous gases in the first gas may come into contact with the composite catalyst within the reactor, whereby the odorous gases are decomposed and removed, thereby generating a second gas from which the odorous gas has been removed. The generated second gas may be discharged to the outside of the reactor. An example of the generated second gas may be odor-removed air (atmospheric atmosphere), but is not limited thereto.

[0087] The first gas and the second gas may be introduced into and discharged from the reaction space by spontaneous flow such as convection without the aid of an external device. Alternatively, the first gas and the second gas may be introduced into and discharged from the reaction space by a conventional device for inducing a gas flow, such as a pump, blower, fan, or the like, which can forcibly introduce and discharge an external fluid.

[0088] The first gas may be, but is not limited to, air inside a sealed device, such as the air inside a refrigerated storage device. For example, the first gas may be air (atmosphere) exposed to a large number of people, requiring forced ventilation, or air (atmosphere) to which vulnerable groups, such as the elderly, are exposed for long periods or repeatedly. More specific examples of the air (atmosphere) include the air (atmosphere) inside buildings such as hospitals, government offices, schools, commercial facilities, and residential facilities, and the air (atmosphere) inside transportation facilities such as subways, buses, and vehicles.

[0089] Due to the high moisture resistance of the composite catalyst, the first gas does not require pretreatment to remove moisture. Therefore, the first gas can contain moisture. For example, the first gas can have a relative humidity of more than 0 and not more than 100%, more preferably 10 to 90%, or even 50 to 90%, and such a moisture-containing first gas can be supplied to the reaction space.

[0090] The following detailed description of the present invention is provided by way of example only and is not intended to limit the scope of the present invention, which is defined solely by the scope of the appended claims.

[0091] <Analysis and evaluation methods> X-ray diffraction analysis X-ray diffraction patterns were measured for the catalyst samples prepared in the examples and comparative examples using an X-ray diffraction analyzer (SmartLab, Rigaku). XRD analysis was performed using Cu-Kα (wavelength = 0.15406 nm) as the X-ray light source using the θ-2θ method at 40 kV, 20 mA, and a scan rate of 5° / min. The maximum intensity value of a corresponding diffraction peak was used as the intensity of a diffraction peak.

[0092] UV-Visible Diffuse Reflectance Spectroscopy (UV-Vis DRS) For UV-Vis DRS, a UV-Vis diffuse reflectance spectrometer (V-770, JASCO Corporation) equipped with an integrating sphere was used. A Spectralon® standard sample was used to set a baseline for calibration, and the light reflected from the catalyst samples prepared in the examples and comparative examples was collected to measure the absorbance of each sample. The thickness of the catalyst samples was 0.5 mm when measuring the absorbance.

[0093] X-ray Photoelectron Spectroscopy (XPS) XPS spectra were measured for the catalyst samples prepared in the examples and comparative examples using an X-ray photoelectron spectrometer (K-Alpha+, Thermo Scientific). Analysis was performed using Al-Kα (1486.6 eV) monochromatic X-ray as the light source under the conditions of a beam diameter of 200 μm, 12 kV, and 10 mA.

[0094] Hydrogen Temperature Programmed Reduction Analysis (H2-Temperature Programmed Reduction, H2-TPR) H2-TPR analysis was performed on the catalyst samples prepared in the examples and comparative examples. For H2-TPR analysis, 0.1 g of catalyst sample was loaded into a 9 mm diameter fixed-bed glass reactor using an AutoChem II 2920 (Micromeritics). Argon gas was flowed at 30 mL / min and the reactor was pretreated at 100 °C for 1 hour. A hydrogen / argon mixed gas with a hydrogen concentration of 10% by volume was then flowed into the glass reactor at 30 mL / min, and the reactor was heated from 100 °C to 800 °C at a rate of 10 °C / min using an electric furnace. The amount of unreacted hydrogen was measured using a thermal conductivity detector (TCD, Micromeritics). The H2-TPR profile was the profile of the TCD signal as a function of temperature (°C). The peaks in the measured H2-TPR profile were defined as the first and second peaks in the order from the low temperature side to the high temperature side, and the highest point of each peak in the H2-TPR profile was defined as the position of the corresponding peak.

[0095] Oxygen Temperature Programmed Desorption (O2-Temperature Programmed Desorption, O2-TPD) An Autochem II 2920 (Micromeritics) was used for O2-TPD analysis. 0.1 g of each catalyst sample was loaded into a 9 mm diameter fixed-bed glass reactor. The reactor was pretreated at 105 °C with helium gas flowing at 30 mL / min for 1 hour and then cooled to 40 °C. Oxygen gas was then flowed at 30 mL / min for 1 hour, followed by purging with helium gas (30 mL / min). Under the appropriate conditions, the temperature was raised to 850 °C at a rate of 10 °C / min, and the amount of desorbed oxygen was measured using a thermal conductivity detector (Micromeritics). The O2-TPD profile is the profile of the TCD signal as a function of temperature (°C). When calculating the area fraction for each temperature range, the baseline was removed from the O2-TPD profile, and the area below the O2-TPD profile was calculated over the entire measured temperature range. The area below the O2-TPD profile in the set temperature range was then calculated, and the area fraction in the corresponding temperature range was calculated.

[0096] Analysis of median diameter based on cumulative volume (D 50 ) 0.1 g of the catalyst sample prepared in the Examples and Comparative Examples was suspended in water, and the suspension was ultrasonicated for 2 minutes. The cumulative volume diameter distribution was then measured using a laser diffraction particle size analyzer (Mastersizer 2000, Malvern Instruments). The median diameter D of the analyte was 50 means the diameter at the position where the cumulative volume is 50% in the cumulative volume diameter distribution.

[0097] Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) The compositions of the catalyst samples prepared in the examples and comparative examples were analyzed using an Avio 220 Max ICP-OES. The catalyst samples were placed in a mixture of equal volumetric ratios of nitric acid, hydrochloric acid, and hydrofluoric acid, and completely dissolved at 180°C. The mixture was then cooled to room temperature and homogenized (diluted) with deionized water. The homogenized solution was then used for ICP-OES measurement.

[0098] specific surface area The catalyst samples prepared in the examples and comparative examples were degassed at 473 K to 20 μTorr for 12 hours, and then subjected to a nitrogen (N2) adsorption-desorption test using a 3Flex adsorption analyzer (Micromeritics) at 77 K. The BET specific surface area of ​​the catalyst samples was calculated using the nitrogen adsorption isotherm and the Brunauer-Emmett-Teller (BET) equation.

[0099] Odor gas removal properties 0.1 g of the composite catalysts according to the examples and comparative examples was packed into a ¼-inch fixed-bed glass reactor. The following gas compositions were supplied to one end of the reactor: 300 sccm of air containing 80 ppm methyl mercaptan, 100 sccm of air containing 10 ppm formaldehyde, 100 sccm of air containing 10 ppm tremethylamine, or 50 sccm of air containing 5 ppm toluene. The other end of the reactor was connected to a GC-MS (Gas Chromatography-Mass Spectroscopy, Agilent) to measure the concentration of odorous gases discharged from the other end of the reactor. For gas removal property experiments, moisture (relative humidity, RH) was supplied by passing air as a carrier through the water-filled reactor (RH 70%). The fixed-bed glass reactor containing the catalyst was maintained at 0°C using an ice jacket. The conversion rate of each gas was calculated using the following formula:

[0100] Conversion(%)=(1-C out / C in )x100 C inis the concentration of the inflowing odorous gas (ppm), C out is the concentration (ppm) of odorous gas after passing through the reaction tube.

[0101] Example 1 900 g of TiO2 (P25, Evonik) was added to 50 L of distilled water and stirred for 15 minutes to prepare a TiO2 dispersion. 300 g of manganese acetate (MnAc2·4H2O, DUKSAN) was added to 25 L of distilled water and stirred for 15 minutes to prepare a manganese precursor aqueous solution. The manganese precursor aqueous solution was then added to the TiO2 dispersion and stirred for 1 hour to prepare a mixture. The pH of the mixture was adjusted to 11.5 by adding an aqueous NaOH solution and stirring for 30 minutes. The pH-adjusted mixture was then vacuum filtered to recover the solids. The recovered solids were heated at a rate of 5°C / min and dried at 120°C for 12 hours. The dried solid powder was heated at a rate of 1.5°C / min and calcined in air at 300°C for 3 hours to prepare composite catalyst 1. The BET specific surface area of ​​composite catalyst 1 is 45.9 m 2 / g, the manganese content of the composite catalyst 1 was 6.7 wt%, and the D 50 was 63 nm.

[0102] Example 2 Composite catalyst 2 was produced in the same manner as in Example 1, except that a KOH aqueous solution was used instead of the NaOH aqueous solution.

[0103] Example 3 Composite catalyst 3 was prepared in the same manner as in Example 1, except that the pH of the mixture was adjusted to 11.0 using an aqueous NaOH solution, and the dried solid powder was calcined at 350°C for 3 hours.

[0104] Example 4 Composite catalyst 4 was prepared in the same manner as in Example 1, except that 800 g of TiO (P25, Evonik) was added to 50 L of distilled water and stirred for 15 minutes to prepare a TiO dispersion, and 600 g of manganese acetate (MnAc·4H O, DUKSAN) was added to 25 L of distilled water and stirred for 15 minutes to prepare a manganese precursor aqueous solution, which was then adjusted to pH 11.0 by adding an NaOH aqueous solution. The manganese content of composite catalyst 4 was 13 wt%.

[0105] Example 5 Composite catalyst 5 was produced in the same manner as in Example 1, except that the solids recovered by vacuum filtration were not immediately dried, but were mixed with 50 L of water, filtered, washed, and then dried and calcined.

[0106] Example 6 Composite catalyst 6 was prepared in the same manner as in Example 1, except that an aqueous ammonia solution (NH4OH solution) was used instead of an aqueous NaOH solution when adjusting the pH of the mixture.

[0107] Example 7 Composite catalyst 7 was prepared in the same manner as in Example 1, except that the pH of the mixed solution was adjusted to 12.5, and the dried solid powder was calcined in air at 400°C for 2 hours.

[0108] (Comparative Example 1) TiO2 (P25, Evonik) was used as the catalyst. Hereinafter, the catalyst of Comparative Example 1 will be collectively referred to as Comparative Catalyst 1. 50 was 62 nm.

[0109] (Comparative Example 2) MnO2 (Sigma Aldrich, Cas No. 1313-13-9) was used as a catalyst. Hereinafter, the catalyst of Comparative Example 2 will be collectively referred to as Comparative Catalyst 2.

[0110] (Comparative Example 3) Solution A was prepared by dissolving 200 g of manganese chloride (MnCl2·4H2O) in 30 L of distilled water and stirring for 15 minutes. Then, 800 g of TiO2 (P25, Evonik) was added to Solution A and stirred for 15 minutes to prepare Solution B. Solution C was prepared by dissolving 200 g of KMnO4 in 20 L of distilled water. Solution C was then slowly added to Solution B at a rate of 50 mL / min to prepare a reaction solution. Ultrasonication was applied to the reaction solution for 30 minutes, followed by heating at 80°C for 12 hours and recovering the precipitate. The recovered precipitate was washed 10 times with 50 L of distilled water, dried at 80°C for 12 hours, and then calcined in air at 300°C for 3 hours to prepare Comparative Catalyst 3.

[0111] Comparative Example 4 900 g of the TiO2 (P25, Evonik) was added to 50 L of distilled water and stirred for 15 minutes to prepare a TiO2 dispersion. 300 g of manganese acetate (MnAc2·4H2O, DUKSAN) was added to 25 L of distilled water and stirred for 15 minutes to prepare a manganese precursor aqueous solution. The manganese precursor aqueous solution was then added to the TiO2 dispersion and stirred for 1 hour to prepare a mixed solution. The mixed solution was dried overnight at 120°C to obtain a dried product. The dried product was then heated at a rate of 1.5°C / min and calcined in air at 500°C for 3 hours to prepare comparative catalyst 4.

[0112] (Comparative Example 5) Comparative catalyst 5 was prepared in the same manner as in Example 1, except that the pH of the mixture was adjusted to a final pH of 9 by slowly adding an aqueous ammonia solution (NHOH solution) instead of an aqueous NaOH solution, and the reaction was continued for 10 hours.

[0113] 1 is a transmission electron microscope photograph of the titanium oxide used as a raw material in the examples (corresponding to comparative catalyst 1, Comparative Example 1 in FIG. 1) and composite catalyst 1 (Example 1 in FIG. 1) prepared in Example 1. As shown in the transmission electron microscope observation results in FIG. 1, no significant differences were found in the shape of the titanium oxide or the size distribution of the primary particles between the titanium oxide used as a raw material and the composite catalyst prepared in Example 1, and no other particles or coatings were substantially observed attached to the surfaces of the titanium oxide primary particles.

[0114] FIG. 2 shows the UV-Vis spectrum of composite catalyst 1 prepared in Example 1, FIG. 3 shows the UV-Vis spectrum of composite catalyst 7 prepared in Example 7, and FIG. 4 shows the UV-Vis spectrum of comparative catalyst 4 prepared in Comparative Example 4. In the UV-Vis spectrum of the catalysts prepared in the examples and comparative examples, the absorbance (A 500 ) at 300 nm wavelength (A 300 ) divided by the ratio (A 500 / A 300 ), and absorbance at 700 nm wavelength (A 700 ) at 300 nm wavelength (A 300 ) divided by the ratio (A 700 / A 300 ) are summarized in Table 1.

[0115] [Table 1]

[0116] 5 shows the H2-TPR profile of composite catalyst 1 produced in Example 1. In the H2-TPR profiles of the catalysts produced in the examples and comparative examples, the peaks positioned in order of increasing temperature were designated as peak 1 and peak 2, and the temperatures at the highest peaks of each peak (the positions of each peak) were designated peak 1 temperature (°C) and peak 2 temperature (°C), which are summarized in Table 2 below. Furthermore, the height (signal intensity) of the highest peak of peak 1 was designated H1, and the height (signal intensity) of the highest peak of peak 2 was designated H2, and the ratio of H1 / H2 was summarized in Table 2.

[0117] [Table 2]

[0118] 6 shows the O 1s XPS spectrum of composite catalyst 1 produced in Example 1. The O 1s XPS spectrum of the catalyst was deconvolved into a lattice oxygen peak (529.2 to 529.9 eV) derived from lattice oxygen, an adsorbed oxygen peak (531.2 to 532.7 eV) derived from surface-adsorbed oxygen, and a hydroxyl peak (532.9 to 533.5 eV) derived from hydroxyl radicals, and was fitted to a Gaussian function for waveform deconvolution. In the O 1s XPS spectra of the catalysts prepared in the examples and comparative examples, the ratio ([O2 + O3] / O1 × 100, %) obtained by dividing the sum of the area of ​​the hydroxy peak (O3) and the area of ​​the adsorbed oxygen peak (O2) by the area of ​​the lattice oxygen peak (O1) was 45 to 85%, and the ratio (O3 / O2 × 100, %) obtained by dividing the area of ​​the hydroxy peak (O3) by the area of ​​the adsorbed oxygen peak (O2) is summarized in Table 3.

[0119] [Table 3]

[0120] 7 shows the O2-TPD profile of the composite catalyst 1 prepared in Example 1. In the O2-TPD profiles of the catalysts prepared in the example and comparative examples, the area fraction (A) of the area integrated under the spectrum in the temperature range of 500-600°C is the total area integrated under the O2-TPD profile measured in the temperature range of 40-850°C. 500-600 ), and the area fraction (A 600-850 ) are summarized in Table 4. 500-600 -A 600-850 ] corresponds to the area fraction of the area obtained by integrating the lower part of the spectrum in the temperature range of 40-500°C.

[0121] [Table 4]

[0122] Fig. 8 shows the X-ray diffraction pattern of composite catalyst 1 produced in Example 1, and Fig. 9 shows the X-ray diffraction pattern of comparative catalyst 4 produced in Comparative Example 4. As shown in the example of Fig. 8, no peaks due to manganese or manganese oxide were detected in the X-ray diffraction patterns of the composite catalysts produced in Examples 1 to 7, but a manganese oxide peak was detected in comparative catalyst 4.

[0123] In all of the composite catalysts produced in Examples 1 to 7, peaks due to the anatase phase and peaks due to the rutile phase were detected. In the X-ray diffraction patterns of the composite catalysts produced in Examples 1 to 7, the maximum intensity I of the diffraction peak (2θ 25.3°) of the (101) plane of the anatase phase was 101 and the maximum intensity I of the diffraction peak (2θ 27.7°) of the (110) plane of the rutile phase. 110 Intensity ratio I 101 / I 110 is in the range of 6.21 to 6.60, which is the same as the intensity ratio (I 101 / I 110 )6.71, which is a similar value.

[0124] In the X-ray diffraction patterns of the composite catalysts produced in Examples 1 to 7 and the titanium oxide (comparative catalyst 1) used as a raw material, the maximum intensity I of the diffraction peak (2θ 25.3°) of the (101) plane of the anatase phase 101 is the maximum intensity of the diffraction peak of the (200) plane of the anatase phase. 200 Intensity ratio (I 101 / I 200 ) are summarized in Table 5 below.

[0125] [Table 5]

[0126] The methyl mercaptan removal performance, formaldehyde removal performance, trimethylamine removal performance, and toluene removal performance of the catalysts prepared in the Examples and Comparative Examples are summarized in Tables 6, 7, 8, and 9. In the tables, RH=0% means a state without moisture (humidity), RH=70% means a state containing moisture (humidity) at a relative humidity of 70%, 5 minutes means the removal efficiency 5 minutes after the odor-containing gas was supplied to the fixed-bed glass reactor, and 1 hour means the removal efficiency 60 minutes after the odor-containing gas was supplied to the fixed-bed glass reactor.

[0127] [Table 6]

[0128] [Table 7]

[0129] [Table 8]

[0130] [Table 9]

[0131] As described above, the present invention has been described using specific and limited examples and drawings, but these are provided merely to facilitate a more comprehensive understanding of the present invention, and the present invention is not limited to the above examples, and those skilled in the art will appreciate that various modifications and variations can be made from such descriptions. Therefore, the scope of the present invention should not be limited to the above examples, and all modifications equivalent to or equivalent to the scope of the appended claims are within the scope of the present invention.

Claims

1. A titanium oxide composite catalyst containing a transition metal including manganese, The composite catalyst contains, on its surface, one or more reactive oxygen species selected from the group consisting of surface-adsorbed oxygen and hydroxyl radicals; In the UV-Vis spectrum, the absorbance (A ５００ ) was calculated by the absorbance (A ３００ ) divided by the ratio (A ５００ / A ３００ ) is 0.85 or more, A composite catalyst in which the hydrogen temperature-programmed reduction profile shows a peak in the temperature range of 240 to 275°C.

2. 2. The composite catalyst of claim 1, wherein the hydrogen temperature-programmed reduction profile has a second peak in a temperature range of 345 to 420°C.

3. The composite catalyst has, in an X-ray photoelectron spectroscopy (XPS) spectrum, a lattice oxygen peak derived from lattice oxygen, an adsorbed oxygen peak derived from surface-adsorbed oxygen, and a hydroxy peak derived from hydroxy radicals; The area of ​​the hydroxy peak (O ３ ) and the area of ​​the adsorbed oxygen peak (O ２ ) is the area of ​​the lattice oxygen peak (O １ ) divided by the ratio ([O ２ +O ３ ] / O １ ×100, %) is 45 to 85%, and the area of ​​the hydroxy peak (O ３ ) is the area of ​​the adsorbed oxygen peak (O ２ ) divided by the ratio (O ３ / O ２ 2. The composite catalyst according to claim 1, wherein x100% is not more than 50%.

4. In the oxygen thermal desorption profile of the composite catalyst, a first area fraction (A ５００－６００ ) is 1 to 20%, and the second area fraction (A ６００－８５０ 2. The composite catalyst according to claim 1, wherein ) is 20-40%.

5. In the X-ray diffraction pattern of the composite catalyst, the intensity of the diffraction peak of the anatase phase (101) plane is I １０１ is the intensity of the diffraction peak of the rutile phase (110) plane, I １１０ Intensity ratio (I １０１ / I １１０ 5. The composite catalyst according to claim 1, wherein ) is 4-8.

6. In the X-ray diffraction pattern of the composite catalyst, the intensity of the diffraction peak of the anatase phase (101) plane is I １０１ is the intensity I of the diffraction peak of the anatase phase (200) plane. ２００ Intensity ratio (I １０１ / I ２００ 6. The composite catalyst according to claim 5, wherein σ is less than or equal to 4.

15.

7. 6. The composite catalyst according to claim 5, wherein the X-ray diffraction pattern does not contain any diffraction peaks due to manganese or manganese oxides.

8. 2. The composite catalyst according to claim 1, wherein the manganese is contained in an amount of 1 to 15 wt %, based on the total weight of the composite catalyst.

9. 2. The composite catalyst of claim 1, wherein said transition metal comprises manganese.

10. The composite catalyst according to claim 1 , wherein the composite catalyst is a catalyst for decomposing volatile organic compounds.

11. An odor gas remover comprising the composite catalyst of claim 1.

12. S1) supplying a first gas containing an odorous gas to a reaction space in which the composite catalyst of claim 1 is located; S2) contacting the odorous gas in the first gas with the composite catalyst to decompose the odorous gas; S3) discharging a second gas produced by decomposing the odorous gas from the reaction space.

13. 13. The method for removing an odorous gas according to claim 12, wherein the odorous gas is any one selected from the group consisting of aldehyde-based compounds, aromatic hydrocarbons, aliphatic hydrocarbons, ammonia-based compounds, and mercaptan-based compounds.

14. The method for removing an odorous gas according to claim 12, wherein in step S1), the first gas contains moisture.

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