Titanium dioxide composite catalyst containing manganese and method for removing odor

Abstract

A composite catalyst according to one disclosure is a titanium dioxide composite catalyst containing a transition metal including manganese, and the composite catalyst contains, in the surface thereof, at least one reactive oxygen species selected from the group consisting of surface-adsorbed oxygen and hydroxy radicals, wherein in the composite catalyst, the ratio (A500 / A300) obtained by dividing the absorbance (A500) at a wavelength of 500 nm by the absorbance (A300) at a wavelength of 300 nm in the UV S-Vis S spectrum is 0.85 or more, and a peak is located in a temperature region of 240 to 275℃ in the hydrogen temperature rise reduction profile. The composite catalyst according to the present invention can effectively remove odors, such as VOC.

Description

Titanium oxide composite catalyst containing manganese and method for removing odor

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

[0002] Various foul odors from the outside environment are emerging as a serious social problem and a source of numerous complaints, necessitating effective treatment methods tailored to each environment. Meanwhile, foul odors in enclosed spaces, such as residential spaces like homes, hotels, and restaurants, or in vehicles like cars and subways, can be unpleasant. These enclosed spaces, where foul odors are emitted, contaminate residents and various items, necessitating technologies that consistently remove these odors to acceptable levels.

[0003] Chemical equipment for odor removal poses safety concerns, making it difficult to install, particularly in enclosed spaces. Therefore, adsorbents are used to remove odors. However, adsorbents have limited adsorption capacity and require regeneration or periodic replacement. However, in practice, regeneration is difficult for consumers, requiring periodic replacement. Furthermore, in enclosed environments where odor emissions are variable, the lifespan of adsorbents is inconsistent, easily contaminating surrounding items with odors, resulting in inconvenience.

[0004] While catalyst-based odor removal technology offers the advantage of not requiring periodic replacement, it suffers from a significant decrease in catalyst activity under conditions such as low temperatures or humid environments, resulting in a very short catalyst lifespan. Consequently, there is a growing need for oxidation catalysts capable of maintaining consistent catalytic activity under a variety of harsh conditions, enabling reliable, long-term odor removal.

[0005] The main problem of the present invention is to provide a catalyst having excellent activity capable of removing harmful gases containing odors under harsh conditions such as a humid environment.

[0006] Another aspect of the present invention is to provide a long-life oxidation catalyst capable of removing odors for a long period of time without an additional regeneration step in a closed environment.

[0007] Another aspect of the present invention is to provide a highly active oxidation catalyst capable of oxidizing various odors containing various types of volatile organic compounds at relatively low temperatures.

[0008] A composite catalyst according to one aspect is a titanium oxide composite catalyst containing a transition metal including manganese, wherein the composite catalyst contains on the surface at least one 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 spectral spectrum. 500 ) at a wavelength of 300 nm, the absorbance (A 300 ) divided by the ratio (A) 500 / A 300 ) is 0.85 or higher, and in the hydrogen temperature reduction profile, the peak is located in the temperature range of 240 to 275°C.

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

[0010] In one specific example, in the X-ray photoelectron spectroscopy (XPS) spectrum of the composite catalyst, the composite catalyst has 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, and a ratio of the sum of the area of ​​the hydroxy peak (O3) and the area of ​​the adsorbed oxygen peak (O2) divided by the area of ​​the lattice oxygen peak (O1) ([O2+ O3] / O1×100, %) is 45 to 85%, and a ratio of the area of ​​the hydroxy peak (O3) divided by the area of ​​the adsorbed oxygen peak (O2) (O3 / O2×100, %) may be 50% or less.

[0011] In one specific example, in the oxygen temperature-elevated desorption profile of the composite catalyst, the first area fraction (A) occupied by the area integrated under the oxygen temperature-elevated desorption profile in the temperature range of 500-600°C is divided by the total area integrated under the oxygen temperature-elevated desorption profile in the temperature range of 40-850°C. 500-600 ) is 1 to 20%, and the second area fraction (A) occupied by the area integrated under the oxygen temperature increase desorption profile in the temperature range of 600-850℃ 600-850 ) can be between 20 and 40%.

[0012] In one specific example, in the X-ray diffraction pattern of the composite catalyst, the intensity I of the diffraction peak of the atanase phase (101) plane 101 The intensity of the diffraction peak I on the (110) side of the rutile 110 Intensity ratio divided by (I 101 / I 110 ) can be 4 to 8.

[0013] In one specific example, in the X-ray diffraction pattern of the composite catalyst, the intensity I of the diffraction peak of the atanase phase (101) plane 101 The intensity of the diffraction peak I on the Athanase (200) plane 200 Intensity ratio divided by (I 101 / I 200 ) may be less than or equal to 4.15.

[0014] In one specific example, the X-ray diffraction pattern may not include diffraction peaks due to manganese and manganese oxide.

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

[0016] In one specific example, the transition metal may be composed of manganese.

[0017] In one specific example, the composite catalyst may be a catalyst for decomposing volatile organic compounds.

[0018] The present invention includes an odor gas remover comprising the composite catalyst described above.

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

[0020] A method for removing an odorous gas according to one aspect comprises the steps of S1) supplying a first gas containing an odorous gas to a reaction space where a titanium oxide composite catalyst containing a transition metal including manganese is positioned; S2) decomposing the odorous gas in the first gas by contacting the composite catalyst; and S3) discharging a second gas generated by decomposition of the odorous gas from the reaction space.

[0021] In one specific example, the malodorous gas may include any one selected from the group consisting of aldehyde compounds, aromatic hydrocarbons, aliphatic hydrocarbons, ammonia compounds, and mercaptan compounds.

[0022] In one specific example, in step S1), the first gas may contain moisture.

[0023] A catalyst according to one embodiment can effectively remove harmful gases containing odors under harsh conditions such as a humid environment.

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

[0025] According to another specific example, a catalyst can effectively oxidize various volatile organic compounds that cause odors at relatively low temperatures.

[0026] A catalyst according to another specific example can effectively remove odorous gases reliably for a long period of time.

[0027] Figure 1 is a transmission electron microscope photograph (scale bar 50 nm) of the titanium oxide used as a raw material in the example and the composite catalyst 1 manufactured in Example 1.

[0028] Figure 2 is a drawing showing the UV-Vis spectral results of composite catalyst 1 manufactured in Example 1.

[0029] Figure 3 is a drawing showing the UV-Vis spectral results of composite catalyst 7 manufactured in Example 7.

[0030] Figure 4 is a drawing showing the UV-Vis spectral results of comparative catalyst 4 manufactured in comparative example 4.

[0031] Figure 5 is a drawing showing the H2-TPR profile of composite catalyst 1 manufactured in Example 1.

[0032] Figure 6 is a drawing showing the O 1s XPS spectrum of composite catalyst 1 manufactured in Example 1.

[0033] Figure 7 is an O2-TPD profile of composite catalyst 1 manufactured in Example 1.

[0034] Figure 8 is an X-ray diffraction pattern of composite catalyst 1 manufactured in Example 1.

[0035] Figure 9 is an X-ray diffraction pattern of comparative catalyst 4 manufactured in comparative example 4.

[0036] Unless otherwise defined, the technical and scientific terms used in this specification have the meaning commonly understood by a person of ordinary skill in the art to which this invention pertains, and descriptions of well-known functions and configurations that may unnecessarily obscure the gist of the present invention are omitted in the following description and accompanying drawings.

[0037] Additionally, the singular forms used herein may be intended to include the plural forms as well, unless the context specifically indicates otherwise.

[0038] In addition, units used in this specification without special mention are based on weight, and for example, units of % or ratio mean weight% or weight ratio, and weight% means the weight% that any one component of the entire composition occupies in the composition unless otherwise defined.

[0039] Additionally, the numerical ranges used herein include lower and upper limits and all values ​​within that range, increments logically derived from the shape and width of the defined range, all doubly defined values, and all possible combinations of upper and lower limits of numerical ranges defined in different shapes. Unless otherwise specifically defined in the specification of the present invention, values ​​outside the numerical range that may arise due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0040] The term "includes" in this specification is an open-ended description equivalent to expressions such as "comprises," "contains," "has," or "characterizes," and does not exclude additional elements, materials, or processes not listed.

[0041] In this specification, when a part such as a film (layer), region, or component is said to be on or above another part, it includes not only cases where it is directly above and in contact with another part, but also cases where another film (layer), another region, another component, etc. is interposed in between.

[0042] In this specification, the pollutant is not particularly limited as long as it is known to cause an unpleasant odor or pollute the air, soil or water, but a more advantageous effect can be obtained for an air pollutant that causes an unpleasant odor. Specifically, the pollutant may be a volatile organic compound (VOC). The VOC may be an aldehyde compound, an aromatic hydrocarbon compound, an aliphatic hydrocarbon compound, an ammonia compound or a mercaptan compound, and specific examples thereof include, but are not limited to, methane, ethylene, formaldehyde, acetaldehyde, toluene, benzene, xylene, ethylene, styrene, ethylbenzene, acetaldehyde, trimethylamine or methyl mercaptan.

[0043] In this specification, titanium oxide may mean titanium dioxide, and may be expressed by the chemical formula TiO2, but does not necessarily mean 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 from 1:2 to some extent due to the inclusion of unavoidable impurities, doping of metal elements, unavoidable defects, and / or adsorbed oxygen species or radicals. As a non-limiting example, titanium oxide is TiO 2-x , and x can be from 0 to 0.5, from 0 to 0.4, from 0 to 0.3, from 0 to 0.2, or from 0 to 0.1.

[0044] Composite catalyst

[0045] A composite catalyst according to one aspect relates to a titanium oxide composite catalyst containing a transition metal including manganese, wherein the composite catalyst contains on its surface at least one 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 a wavelength of 300 nm, the absorbance (A 300 ) divided by the ratio (A) 500 / A300 ) is 0.85 or higher, and in the hydrogen temperature reduction profile, the peak is located in the temperature range of 240 to 275°C.

[0046] A in UV-Vis spectral spectrum 500 / A 300 Since 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 reduction profile, the composite catalyst can have both high activity and moisture resistance.

[0047] Advantageously, A in UV-Vis spectral spectrum 500 / A 300 The value can be greater than or equal to 0.87, greater than or equal to 0.89, greater than or equal to 0.90, greater than or equal to 0.91, greater than or equal to 0.92, or greater than or equal to 0.93, and practically less than or equal to 1.00 or less than or equal to 0.98. As an advantageous and practical example, A 500 / A 300 The value may be 0.90 to 0.98, 0.92 to 0.98, or 0.93 to 0.98. More advantageously, the composite catalyst may be the above-mentioned A 500 / A 300 At the same time, the absorbance at 700 nm wavelength in the UV-Vis spectral spectrum (A 700 ) at a wavelength of 300 nm, the absorbance (A 300 ) divided by the ratio (A) 700 / A 300 ) may be 0.85 to 0.97, specifically 0.87 to 0.95.

[0048] The size and position of the peak in the hydrogen temperature programmed reduction (H2-TPR) profile may be properties determined by the oxidation number of manganese (manganese ion) contained in the composite catalyst, the activity level of manganese (manganese ion) having a specific oxidation number, and the content level of manganese (manganese ion) having a specific oxidation number.

[0049] In the H2-TPR profile of the composite catalyst, together with the UV-Vis spectroscopy spectrum described above, the peak is located in the low temperature region of 240 to 275°C, indicating that the composite catalyst can have high activity for removing pollutants, especially mercaptan compounds, while also having improved moisture resistance.

[0050] Advantageously, the peak in the H2-TPR profile of the composite catalyst may be located in the temperature range of 245 to 275°C, more advantageously 250 to 275°C. In such cases, the composite catalyst may have improved moisture resistance along with high activity.

[0051] In the H2-TPR profile of the composite catalyst, the peak located in the temperature range of 240 to 275°C described above is set 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 a peak due to manganese (manganese ion) having a higher oxidation number, and the second peak may be a peak due to manganese (manganese ion) having a lower oxidation number. Since the second peak in the H2-TPR profile is located in the temperature range of 345 to 420°C, advantageously 345 to 380°C, and more advantageously 350 to 380°C, the composite catalyst may have high activity and long-term moisture resistance.

[0052] Although not necessarily limited to this interpretation, in order to simultaneously secure high activity and long-term moisture stability, it can be interpreted that both activity for removing pollutants and long-term moisture stability are simultaneously secured when manganese doped in the lattice sites, defect sites, and interstitial sites within the titanium oxide has the instability to effectively act as an active site or causes instability in the surrounding titanium oxide structure while simultaneously suppressing excessive instability. The degree of instability possessed by or caused by the aforementioned manganese can be represented by the temperature of the first peak of the H2-TPR profile, further by the temperature of the first peak and the temperature of the second peak, further by the temperature of the first peak and the temperature of the second peak, and the ratio of the height of the first peak (H1) to the height of the second peak (H2) (H1 / H2).

[0053] In an advantageous example, while satisfying the temperature of the first peak and the temperature of the second peak as described above, in the H2-TPR profile, the ratio (H1 / H2) of the height of the first peak (H1) to the height of the second peak (H2) may be 0.5 or more, specifically 0.5 to 5.0, advantageously, H1 / H2 may be 2.0 to 5.0. In the H2-TPR profile as described above, the position of a peak may mean the position at 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.

[0054] 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, and a first area 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) is 45 to 85%, and a second area ratio (O3 / O2×100, %) obtained by dividing the area of ​​the hydroxy peak (O3) by the area of ​​the adsorbed oxygen peak (O2) may be 50% or less, specifically 10 to 50%.

[0055] Since the composite catalyst satisfies the first area ratio of 45 to 85% and the second area ratio of 50% or less, specifically the second area ratio of 5 to 50% or less in the XPS O 1s spectrum, the composite catalyst can exhibit high oxidation activity against various odor-causing VOCs, such as aldehyde compounds, aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, ammonia compounds, or mercaptan compounds, among pollutants.

[0056] 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 for pollutants, specifically VOCs that cause malodor, and can be interpreted as having a large amount of surface-adsorbed oxygen and hydroxyl radicals, but with surface-adsorbed oxygen being more advantageous than hydroxyl radicals in improving the oxidation ability for various VOCs.

[0057] In an advantageous example, the first area ratio may be 60 to 80%, and the second area ratio may be 10 to 30%, while satisfying the aforementioned UV-Vis spectral properties and H2-TPR profile characteristics.

[0058] 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. The composite catalyst satisfying these properties exhibits high oxidation activity against various VOCs, excellent moisture resistance, and can exhibit enhanced oxidation activity even at low temperatures where a large amount of moisture is present.

[0059] In the O2-Temperature Programmed Desorption (O2-TPD) profile, the composite catalyst has a first area fraction (A) occupied by the area under the O2-TPD profile measured in the temperature range of 40-850°C, divided by the total area under the O2-TPD profile measured 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) occupied by the area integrated under the O2-TPD profile in the temperature range of 600-850℃ 600-850 ) can be 20 to 40%, specifically 20 to 30%.

[0060] Although not necessarily limited to this interpretation, in the O2-TPD profile, the temperature ranges of 500 to 600°C and 600 to 850°C can be interpreted as indicating the instability of lattice oxygen including the surface-adjacent region of the composite catalyst, or in other words, the crystallographic stability in the internal region of the composite catalyst including the surface-adjacent region.

[0061] Since 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 high activity, thereby having improved durability.

[0062] The composite catalyst can satisfy the aforementioned UV-Vis spectral properties and H2-TPR profile characteristics, as well as the aforementioned O2-TPD properties. A composite catalyst satisfying these properties can exhibit high activity, enhanced moisture resistance, and improved durability. This enhanced durability allows for the stable, long-term maintenance of excellent catalytic activity over a wide temperature range.

[0063] The composite catalyst may contain titanium dioxide crystallographically in the anatase phase, and advantageously, may contain both anatase and rutile phases of titanium dioxide. The anatase and rutile crystal phases can be identified through X-ray diffraction analysis, and if there is one or more diffraction peaks corresponding to the diffraction peak positions(s) of anatase and rutile titanium dioxide defined in JCPDS, the composite catalyst may be defined as containing the anatase and rutile crystal phases. The crystal size based on the X-ray diffraction pattern in the composite catalyst may be, but is not limited to, on the order of 10 to 40 nm.

[0064] The relative contents of the anatase phase and the rutile phase contained in the composite catalyst are determined by the maximum intensity I of the (101) plane diffraction peak of the anatase phase in the X-ray diffraction pattern. 101 The maximum intensity of the (110) plane diffraction peak (2θ 27.7°) of the rutile phase I 110 Intensity ratio I 101 / I 110 can be directed to. In a favorable example, I 101 / I 110The content may be 4 to 8, advantageously 5 to 7, and more advantageously 6 to 7. A composite titanium oxide in which anatase and rutile phases are mixed in such a content is advantageous because it can further improve the catalytic performance by the synergistic effect of the two phases. However, it should not be interpreted 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 include titanium oxide in a brookite phase and / or an amorphous phase.

[0065] X-ray diffraction patterns can represent the macroscopic properties of the crystallinity of composite catalysts. The degree of crystallographic deformation / distortion caused by doping of transition metals including manganese while the titanium oxide, which is the matrix for doping in the composite catalyst, maintains stable crystallinity is determined by the maximum intensity I of the (101) plane diffraction peak (2θ 25.3°) of the anatase phase in the X-ray diffraction pattern of the composite catalyst. 101 The maximum intensity of the diffraction peak I on the Athanase (200) plane 200 Intensity ratio divided by (I 101 / I 200 ) can be measured. In one specific example, I 101 / I 200 may be 4.15 or less, specifically 2.50 to 4.15, and more specifically 2.50 to 4.10.

[0066] 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). As an advantageous example, the composite catalyst may include a titanium oxide doped with a transition metal including manganese. As a practical example, the composite catalyst may be a composite catalyst including a manganese-doped titanium oxide, or a composite catalyst including a 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) together with manganese.

[0067] The composite catalyst may have the shape of particles, and the average particle diameter of the particles is D 50 can be defined as, and the average particle diameter is not limited to a specific range. The average particle diameter is the volume-based median diameter (D) calculated by laser diffraction method. 50 ) can mean volume criterion D 50 It means the particle diameter at the point where the cumulative volume % is 50% in the cumulative distribution curve (cumulative distribution curve) accumulated in order of particle diameter. Experimentally, D 50 The cumulative distribution curve including can be obtained by a conventional particle size analyzer using a laser diffraction method or a dynamic light scattering method.

[0068] D of composite catalysts in particle shape 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, or 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.

[0069] The BET surface area of ​​the composite catalyst is 40 to 60 m 2 / g, specifically 40 to 55 m 2 / g, more specifically 40 to 50 m 2 / g may be.

[0070] 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%.

[0071] A composite catalyst according to one embodiment may be effective in the decomposition or removal of pollutants. One example of decomposition or removal of pollutants may be oxidation of pollutants, which involves converting pollutants into other environmentally safe chemical species through a catalytic oxidation reaction using a composite catalyst according to one embodiment.

[0072] The composite catalyst can decompose pollutants at low, medium, and high temperature ranges. Specifically, it can effectively decompose pollutants at low temperatures ranging from -20 to 10°C, medium temperatures ranging from 10 to 100°C, and high temperatures ranging from 100 to 300°C.

[0073] According to one embodiment, the composite catalyst exhibits excellent long-term activity, maintaining relatively constant catalytic activity even in low-temperature and humid environments, eliminating the need for additional catalyst regeneration steps. Because the composite catalyst exhibits excellent long-term activity, it can continuously oxidize and remove pollutants even in a closed environment where pollutants are continuously generated. Therefore, simply installing the composite catalyst in a specific space within the closed environment can effectively suppress pollutant contamination of the closed environment.

[0074] <Method for producing a composite catalyst>

[0075] One aspect of the present invention relates to a method for preparing a titanium oxide composite catalyst containing a transition metal including manganese, and relates to the method for preparing the composite catalyst of the aforementioned embodiment. Accordingly, the method for preparing the composite catalyst includes all of the contents described above for the composite catalyst.

[0076] A method for producing a composite catalyst according to one embodiment comprises: 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) preparing a mixture by mixing the dispersion and the precursor solution; 4) adjusting the pH of the mixture to a strongly basic range of 10.5 to 12.5; and 5) vacuum filtering the mixture in which the pH is adjusted to a strongly 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.

[0077] Step 1) is a step of preparing a dispersion by dispersing titanium oxide particles in a solvent, and step 2) is a step of preparing a precursor solution by dissolving a transition metal precursor including a manganese precursor in a solvent. The solvent of step S1) and the solvent of step 2) may independently be polar solvents, specifically polar protic solvents. For example, the solvent of step 1) and the solvent of step 2) may independently be (C1-C7) alcohol, water, or a cosolvent thereof, specifically (C1-C4) alcohol, water (including deionized water), or a cosolvent thereof, and more specifically water.

[0078] 1) The titanium oxide particles of the step may be titanium oxide particles in which anatase phase and rutile phase are advantageously mixed. D of the titanium oxide particles 50The particle size may be 0.01 ㎛ or more, 0.05 ㎛ or more, 0.1 ㎛ or more, 0.2 ㎛ or more, 0.3 ㎛ or more, 0.4 ㎛ or more, 0.5 ㎛ or more, 0.7 ㎛ or more, 0.8 ㎛ or more, or 1 ㎛ or more, and may be 1000 ㎛ or less, 800 ㎛ or less, 700 ㎛ or less, 500 ㎛ or less, 100 ㎛ or less, 50 ㎛ or less, 1 ㎛ or less, 0.5 ㎛ or less, or 0.1 ㎛ or less. For example, it may be 0.01 ㎛ to 1000 ㎛, 0.05 ㎛ to 0.5 ㎛, 1 ㎛ to 500 ㎛, 0.01 ㎛ to 0.1 ㎛, or 0.01 ㎛ to 1 ㎛, but is not limited thereto. Titanium oxide particles can be commercially produced in a mixture of anatase and rutile phases. A representative example of such commercial products is P25 (Evonik).

[0079] 2) The transition metal precursor comprising the manganese precursor of step 2 may be a transition metal compound that is soluble in a polar solvent, specifically, a polar protic solvent. As an example based on manganese, the precursor may be one or a combination of two or more selected from the group consisting of manganese acetate (Mn(Ac)2), manganese nitrate (Mn(NO3)2), manganese chloride (MnCl2), manganese acetylacetonate (Mn(acac)2) and hydrates thereof. Advantageously, the manganese precursor may be one or more selected from the organic-based precursors manganese acetate and manganese acetylacetonate.

[0080] 1) The dispersion of step may contain 0.1 to 5 wt%, specifically 0.5 to 4 wt%, of titanium oxide particles, and 2) the precursor solution of step may contain 0.1 to 5 wt%, specifically 0.3 to 3 wt%, of a transition metal precursor, but is not necessarily limited thereto.

[0081] A transition metal precursor including a manganese precursor can be mixed with a titanium oxide dispersed in a solvent while being dissolved in a solvent. In step 3), the mixing between the dispersion and the precursor solution can be performed in consideration of the mass of the titanium oxide contained in the precursor solution and the mass of the transition metal including manganese contained in the precursor solution, and the mixture can be performed such that the transition metal satisfies a range of 1 to 15 wt%, advantageously a range of 1 to 10 wt%, and more advantageously a range of 4 to 9 wt%, based on the total weight of the titanium oxide and the transition metal.

[0082] 4) In step 4), the mixed solution can be adjusted to a pH of 11.0 to 12.5, advantageously a strongly basic range of 11.0 to 12.0, using a pH adjuster. The pH adjuster can be introduced into the mixed solution in a state dissolved in a polar protic solvent, for example, water. The pH adjuster can be a base such as ammonia, an amine compound, a quaternary ammonium compound, an alkali metal hydroxide, or an alkaline earth metal hydroxide, and is preferably an alkali metal hydroxide, more preferably NaOH or KOH, and even more preferably NaOH. The mixed solution whose pH is adjusted to a strongly basic range can be stirred for 10 to 60 minutes, specifically, for 20 to 50 minutes, but is not limited thereto.

[0083] Step 5) is a step for separating and recovering the solid from the mixed solution in which the reaction has been completed. To separate and recover the solid, any separation means known in the art, such as filtration or centrifugation, can be selected without limitation.

[0084] The recovered solid can be dried and calcined in step 6), so that a composite catalyst containing manganese can be produced. The drying in step 6) can be performed at a temperature of 100 to 200°C, specifically 100 to 150°C. The drying time can be 2 to 24 hours, but is not limited thereto. The calcination in step 6) can be performed at a temperature of 250 to 400°C, advantageously 300 to 350°C, for 2 to 4 hours. The calcination of the dried solid can be performed in the air, and the temperature increase rate during drying or calcination can be 1 to 10°C / min, but is not necessarily limited thereto.

[0085] The solid recovered from the mixed solution can be dried in a state in which it is washed with water before drying or in a state in which it is not washed, and advantageously, it can be dried in a state in which it is recovered by solid-liquid separation such as filtration without being washed.

[0086] Odor gas remover

[0087] Another aspect of the present invention relates to a malodorous gas remover comprising a titanium oxide composite catalyst containing a transition metal including manganese. The malodorous gas remover may comprise the composite catalyst of the aforementioned embodiment. Accordingly, the malodorous gas remover comprises all of the properties described above for the composite catalyst.

[0088] In one specific example, the malodorous gas remover may be a composite catalyst. The malodorous gas remover may include composite catalyst particles (powder), aggregates of particulate composite catalysts, or a molded body in which the composite catalyst is molded into a desired shape. In this case, the shape of the molded body in which the composite catalyst is molded may be any shape commonly used in the field of removing malodorous gases using catalysts. Practical examples of the molded body include, but are not limited to, bulk shapes, spherical particle shapes, cylindrical or ring-shaped pellet shapes, honeycomb shapes, fiber shapes, etc.

[0089] In one specific example, the malodorous gas remover may be a coated product in which the above-described 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, etc.; a carbon-based support such as activated carbon, etc.; or an organic support such as a synthetic resin, a natural polymer, a biocompatible polymer, a thermosetting resin, a thermoplastic resin, or a mixed resin thereof, etc. The shape of the support is not particularly limited, but may include a honeycomb shape, a spherical, cylindrical or ring-shaped pellet shape, a plate shape, a porous mesh or porous foam shape, a woven or non-woven fiber shape, etc. As a more practical example, the malodorous gas remover may include a fabric, filter, film or fiber, etc. in which the above-described composite catalyst is contained on the surface or inside. In this case, the filter may be a gas treatment filter, and the gas may include air (atmosphere), etc.

[0090] The odor gas remover can be manufactured by a method commonly used for coating a catalyst material on a support, such as immersion, spraying, or slurry coating, and 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. At this time, it goes without saying that a binder component can be used to stably fix the composite catalyst to the support, if necessary.

[0091] <Products with the ability to remove odorous gases>

[0092] Another aspect of the present invention relates to a product comprising a titanium oxide composite catalyst containing a transition metal, including manganese. A product capable of removing odorous gases by means of a composite catalyst may comprise the composite catalyst of the aforementioned embodiment. Accordingly, the product includes all of the features described above regarding the composite catalyst.

[0093] An article having an odor gas removal capability may be an article that requires odor gas removal properties and includes the aforementioned composite catalyst or the aforementioned odor gas removal agent on the surface of the article or in a predetermined space of the article. In cases where the composite catalyst is contained on the surface, examples thereof include an article body having a surface area formed by the composite catalyst, or an article body having a coating layer containing the composite catalyst formed on any surface of the article body.

[0094] A practical example of an article having the ability to remove odor gases is a storage device equipped with a composite catalyst or the aforementioned odor gas remover and storing food, medicine, industrial products, etc., and a more practical example is a refrigerated storage device.

[0095] <Method for removing foul-smelling gases>

[0096] One aspect of the present invention relates to a method for removing a malodorous gas, comprising the steps of: S1) supplying a first gas containing a malodorous gas to a reaction space where a titanium oxide composite catalyst containing a transition metal including manganese is positioned; S2) contacting the malodorous gas in the first gas with the composite catalyst to decompose the malodorous gas; and S3) discharging a second gas generated by decomposition of the malodorous gas from the reaction space. The method for removing a malodorous gas comprises ... all of the above-described contents of the composite catalyst.

[0097] The composite catalyst within the reaction space may be a fluidized bed or a fixed bed, and as a practical example, a predetermined area of ​​the reaction space may be filled with the composite catalyst or the composite catalyst in the form of the aforementioned odor gas remover.

[0098] The first gas may be, but is not necessarily limited to, air (atmosphere) containing an odorous gas.

[0099] The reaction space may be an open space into which a first gas may be introduced and a second gas may be discharged. The open space may be implemented through opening(s) that connect the inside and the outside of the reactor that defines the reaction space, but is not necessarily limited thereto. A composite catalyst may be positioned inside the reactor, and a first gas may be introduced into the reactor. The odorous gas in the introduced first gas may come into contact with the composite catalyst inside the reactor, thereby decomposing and removing the odorous gas, and generating a second gas from which the odorous gas has been removed. The generated second gas may be discharged outside the reactor. Examples of the generated second gas include, but are not limited to, air (atmosphere) from which the odor has been removed.

[0100] The first and second gases can be introduced and discharged into the reaction space by spontaneous flow, such as convection, without the assistance of external devices. Alternatively, the first and second gases can be introduced and discharged into the reaction space by devices that induce conventional gas flow, such as pumps, blowers, or fans that can forcibly introduce and discharge external fluids.

[0101] The primary gas may be, but is not limited to, the air within a sealed device, such as the air inside a refrigerated storage device. For example, the primary gas may be air (atmosphere) to which a large number of people are exposed, air (atmosphere) that requires forced ventilation, or air (atmosphere) to which vulnerable populations, such as the elderly, are exposed for long periods or repeatedly. More specifically, the primary gas may be air (atmosphere) within buildings, such as hospitals, government offices, schools, commercial facilities, and residential facilities, or air (atmosphere) within transportation facilities, such as subways, buses, and vehicles.

[0102] Due to the high moisture resistance of the composite catalyst described above, the first gas does not require pretreatment to remove moisture. Accordingly, the first gas may contain moisture. For example, the first gas may have a relative humidity of more than 0 and less than 100%, more practically a relative humidity of 10 to 90%, or even 50 to 90%. The first gas containing such moisture may be supplied to the reaction space.

[0103] Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples and the present invention is not limited thereto, and the present invention is defined solely by the scope of the claims set forth below.

[0104] <Analysis and Evaluation Method>

[0105] X-ray diffraction analysis

[0106] For the catalyst samples manufactured in the examples and comparative examples, X-ray diffraction patterns were measured using an X-ray diffraction analyzer (SmartLab, Rigaku). XRD analysis was performed using Cu-Kα (wavelength = 0.15406 nm) as an X-ray light source by the θ-2θ method, and was performed under the conditions of 40 kV, 20 mA, and 5° / min scan rate. The maximum intensity value of the corresponding diffraction peak was used as the intensity of a single diffraction peak.

[0107] Ultraviolet-Visible Diffuse Reflectance Spectroscopy (UV-Vis DRS)

[0108] UV-Vis DRS was performed using a UV-Vis diffuse reflectance spectrometer (V-770, JASCO) equipped with an integrating sphere. Spectralon was used for baseline correction. ®A baseline was established using a standard sample, and the light reflected from the catalyst samples manufactured in the examples and comparative examples was collected to measure the absorbance of each sample. The thickness of the catalyst sample at the time of absorbance measurement was 0.5 mm.

[0109] X-ray photoelectron spectroscopy (XPS)

[0110] XPS spectra were measured for the catalyst samples manufactured in the examples and comparative examples using an X-ray photoelectron spectroscopy analyzer (K-Alpha+, Thermo scientific). Monochromatic X-rays of Al-Kα (1486.6 ev) were used as a light source, and analysis was performed under conditions of a beam diameter of 200 μm, 12 kV, and 10 mA.

[0111] Hydrogen Temperature Programmed Reduction (H2-TPR)

[0112] H2-TPR analysis was performed on the catalyst samples manufactured in the examples and comparative examples. For the analysis of H2-TPR, AutoChem II 2920 (Micromeritics) was used, and 0.1 g of the catalyst sample was charged into a fixed-bed glass reactor with a diameter of 9 mm, and argon gas was flowed at 30 ml / min, and the reactor was pretreated at 100°C for 1 hour. Afterwards, a hydrogen / argon mixture gas with a hydrogen concentration of 10% by volume was flowed at 30 ml / min into the glass reactor, 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 is the profile of the TCD signal according to temperature (°C). The peaks located in the measured H2-TPR profile were sequentially defined as the first peak and the second peak in the direction 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.

[0113] O2-Temperature Programmed Desorption (O2-TPD)

[0114] For the analysis of O2-TPD, Autochem II 2920 (Micromeritics) was used. 0.1 g of each catalyst sample was charged into a fixed-bed glass reactor with a diameter of 9 mm, and the glass reactor was pretreated at 105°C for 1 h under a helium gas flow of 30 ml / min, and then cooled to 40°C. Afterwards, oxygen gas was flowed at 30 ml / min for 1 h, and then purged with helium gas (30 ml / min). Under these conditions, the temperature was increased at a rate of 10°C / min to 850°C, and the amount of oxygen desorbed was measured using a thermal conductivity gas analyzer (Thermal Conductivity Detector, Micromertics). The O2-TPD profile is the profile of the TCD signal according to temperature (°C). When calculating the area fraction by temperature region, after removing the baseline from the O2-TPD profile, the area under the O2-TPD profile in the entire measured temperature region was calculated, and the area under the O2-TPD profile in the set temperature region was calculated to calculate the area fraction in the corresponding temperature region.

[0115] Cumulative volume-based median diameter analysis (D 50 )

[0116] 0.1 g of the catalyst samples manufactured in the examples and comparative examples were suspended in water, and the manufactured suspension was sonicated for 2 minutes, and then the cumulative volume diameter distribution was measured using a laser diffraction particle size distribution measuring device (Mastersizer 2000, Malvern Instruments). The median diameter D of the target material was measured. 50 In the cumulative volume diameter distribution, it refers to the diameter at the location where the cumulative volume is 50%.

[0117] Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES)

[0118] The composition of the catalyst samples manufactured in the examples and comparative examples was analyzed using an Avio 220 Max ICP-OES. The catalyst samples were added to a mixture of nitric acid, hydrochloric acid, and hydrofluoric acid in equal volume ratios, completely dissolved at 180°C, cooled to room temperature, homogenized (diluted) by mixing with deionized water, and the homogenized solution was used for ICP-OES measurement.

[0119] specific surface area

[0120] The catalyst samples manufactured in the examples and comparative examples were degassed at 473 K to 20 μTorr for 12 hours, and then nitrogen (N2) adsorption-desorption tests were performed at 77 K using a 3Flex adsorption analyzer (Micromeritics). At this time, the BET specific surface area of ​​the catalyst samples was obtained using the nitrogen adsorption isotherm and the Brunauer-Emmett-Teller (BET) equation.

[0121] Odor gas removal properties

[0122] 0.1 g of the composite catalyst according to the examples and comparative examples was charged into a 1 / 4 inch fixed bed glass reaction tube, and 300 sccm of Air gas containing 80 ppm of methyl mercaptoethanol, 100 sccm of Air gas containing 10 ppm of formaldehyde, 100 sccm of Air gas containing 10 ppm of trimethylamine, or 50 sccm of Air gas containing 5 ppm of toluene was supplied to one end of the reaction tube, and the other end of the reaction tube was connected to GC-MS (Gas Chromatography-Mass Spectroscopy, Agilent) to measure the concentration of odorous gas emitted from the other end of the reaction tube. In the gas removal characteristic experiment, moisture supply (relative humidity, RH) was supplied (RH 70%) by passing the carrier air gas through a reactor filled with water, and the fixed-bed glass reactor equipped with a catalyst was maintained at 0℃ using an ice jacket, and the removal rate (conversion) of each gas was calculated according to the following equation.

[0123] Conversion (%) = (1-C out / C in ) x 100

[0124] C in is the concentration of incoming odorous gas (ppm), C out is the concentration (ppm) of odorous gas after passing through the reaction tube.

[0125] (Example 1)

[0126] TiO2 (P25, Evonik) 900 g was added to 50 L of distilled water and stirred for 15 minutes to prepare a TiO2 dispersion, and manganese acetate (MnAc₂·4H₂O, Deoksan) 300 g was added to 25 L of distilled water and stirred for 15 minutes to prepare a manganese precursor aqueous solution. Then, the prepared manganese precursor aqueous solution was added to the TiO2 dispersion and stirred for 1 hour to prepare a mixed solution. NaOH aqueous solution was added to the prepared mixed solution to adjust the pH to 11.5 and stirred for 30 minutes. After that, the pH-adjusted mixed solution was vacuum-filtered to recover the solid content, and the recovered solid content was dried at 120°C for 12 hours by heating it at a rate of 5°C / min. 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 surface area of ​​composite catalyst 1 is 45.9 m 2 / g, the manganese content of composite catalyst 1 was 6.7 wt%, and D of composite catalyst 1 50 was 63nm.

[0127] (Example 2)

[0128] Composite catalyst 2 was prepared in the same manner as in Example 1, except that a KOH aqueous solution was used instead of a NaOH aqueous solution in the above Example 1.

[0129] (Example 3)

[0130] Composite catalyst 3 was manufactured 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.

[0131] (Example 4)

[0132] In the above Example 1, 800 g of TiO2 (P25, Evonik) was added to 50 L of distilled water and stirred for 15 minutes to prepare a TiO2 dispersion, 600 g of manganese acetate (MnAc₂·4H₂O, Deoksan) was added to 25 L of distilled water and stirred for 15 minutes to prepare a manganese precursor aqueous solution, and NaOH aqueous solution was added to adjust the pH to 11.0, except that the same procedure as Example 1 was followed to prepare a composite catalyst 4. The manganese content of the composite catalyst 4 was 13 wt%.

[0133] (Example 5)

[0134] In the above Example 1, a composite catalyst 5 was manufactured in the same manner as in Example 1, except that the recovered solid was not immediately dried by vacuum filtration, but was mixed with 50 L of water, filtered, washed, and then dried and calcined.

[0135] (Example 6)

[0136] In the above Example 1, a composite catalyst 6 was manufactured in the same manner as in Example 1, except that an ammonia aqueous solution (NH4OH solution) was used instead of a NaOH aqueous solution when adjusting the pH of the mixed solution.

[0137] (Example 7)

[0138] In the above Example 1, a composite catalyst 7 was manufactured in the same manner as in Example 1, except that the pH of the mixture was controlled to 12.5 and the dried solid powder was calcined in the air at 400°C for 2 hours.

[0139] (Comparative Example 1)

[0140] TiO2 (P25, Evonik) was used as a catalyst. Hereinafter, the catalyst of Comparative Example 1 is collectively referred to as Comparative Catalyst 1. D of Comparative Catalyst 1 50 was 62nm.

[0141] (Comparative Example 2)

[0142] MnO2 (Sigma Aldrich, Cas No. 1313-13-9) was used as a catalyst. Hereinafter, the catalyst of Comparative Example 2 is collectively referred to as Comparative Catalyst 2.

[0143] (Comparative Example 3)

[0144] 200 g of manganese chloride (MnCl₂·4H₂O) was dissolved in 30 L of distilled water and stirred for 15 minutes to prepare Solution A. Then, 800 g of TiO₂ (P25, Evonik) was added to Solution A and stirred for 15 minutes to prepare Solution B. 200 g of KMnO₄ was dissolved in 20 L of distilled water to prepare Solution C. Afterwards, Solution C was slowly added to Solution B at a rate of 50 ml / min to prepare a reaction solution. Ultrasonic waves were applied to the reaction solution for 30 minutes, and then heated at 80°C for 12 hours and the precipitate was recovered. The recovered precipitate was washed 10 times with 50 L of distilled water, dried at 80°C for 12 hours, and calcined in air at 300°C for 3 hours to prepare Comparative Catalyst 3.

[0145] (Comparative Example 4)

[0146] 900 g of the above TiO2 (P25, Evonik) was added to 50 L of distilled water and stirred for 15 minutes to prepare a TiO2 dispersion, and 300 g of manganese acetate (MnAc₂·4H₂O, Deoksan) was added to 25 L of distilled water and stirred for 15 minutes to prepare a manganese precursor aqueous solution. Thereafter, the prepared manganese precursor aqueous solution was added to the TiO2 dispersion and stirred for 1 hour to prepare a mixed solution. The prepared mixed solution was dried at 120°C overnight to obtain a dried product, and the obtained dried product was heated at a rate of 1.5°C / min and calcined in air at 500°C for 3 hours to prepare Comparative Catalyst 4.

[0147] (Comparative Example 5)

[0148] In the above Example 1, when adjusting the pH of the mixed solution, an ammonia aqueous solution (NH4OH solution) was slowly added instead of an NaOH aqueous solution to finally reach pH 9, and the reaction was carried out for 10 hours, and the same procedure as Example 1 was performed to manufacture a comparative catalyst 5.

[0149] Fig. 1 is a transmission electron microscope photograph of the titanium oxide used as a raw material in the example (corresponding to comparative catalyst 1, Comparative Example 1 in Fig. 1) and the composite catalyst 1 manufactured in Example 1 (Example 1 in Fig. 1). As shown in the transmission electron microscope observation results in Fig. 1, no significant difference was found in the shape or primary particle size distribution of the titanium oxide between the titanium oxide used as a raw material and the composite catalyst manufactured in Example 1, and practically no heterogeneous particles or coatings adhered to the surface of the titanium oxide primary particles were observed.

[0150] Figure 2 is a drawing showing the UV-Vis spectral result of the composite catalyst 1 manufactured in Example 1, Figure 3 is a drawing showing the UV-Vis spectral result of the composite catalyst 7 manufactured in Example 7, and Figure 4 is a drawing showing the UV-Vis spectral result of the comparative catalyst 4 manufactured in Comparative Example 4. The absorbance (A) at a wavelength of 500 nm in the UV-Vis spectral spectra of the catalysts manufactured in the Examples and Comparative Examples 500 ) at a wavelength of 300 nm, the absorbance (A 300 ) divided by the ratio (A) 500 / A 300 ) and absorbance at a wavelength of 700 nm (A 700 ) at a wavelength of 300 nm, the absorbance (A 300 ) divided by the ratio (A) 700 / A 300 ) are summarized in Table 1.

[0151] A 500 / A 300 A 700 / A 300 A 500 / A 300 A 700 / A300 Composite catalyst 10.970.94Composite catalyst 70.880.86Composite catalyst 20.930.89Comparative catalyst 10.230.25Composite catalyst 30.930.91Comparative catalyst 20.970.98Composite catalyst 40.930.89Comparative catalyst 30.630.70Composite catalyst 50.940.91Comparative catalyst 40.890.85Composite catalyst 60.920.89Comparative catalyst 50.900.86

[0152] FIG. 5 is a diagram illustrating the H2-TPR profile of the composite catalyst 1 manufactured in Example 1. In the H2-TPR profile of the catalysts manufactured in the Examples and Comparative Examples, the peaks sequentially positioned in the direction of increasing temperature are designated as the first peak and the second peak, and the temperature at the highest peak of each peak (the position of each peak) is designated as the first peak temperature (℃) and the second peak temperature (℃), and these are summarized in Table 2 below. In addition, the height (signal intensity) of the highest peak of the first peak is designated as H1, and the height (signal intensity) of the highest peak of the second peak is designated as H2, and the ratio of H1 / H2 is summarized in Table 2.

[0153] First peak temperatureSecond peak temperatureH1 / H2Composite catalyst 1263.3369.94.6Composite catalyst 2250.1376.92.0Composite catalyst 3273.2365.02.8Composite catalyst 4268.5374.62.7Composite catalyst 5246.1348.12.7Composite catalyst 6254.5361.32.6Composite catalyst 7246.4417.20.8Composite catalyst 1---Composite catalyst 2344.0536.60.4Composite catalyst 3418.6531.40.3Composite catalyst 4287.8380.80.9Composite catalyst 5238.3351.01.2

[0154] Figure 6 is a diagram illustrating the O 1s XPS spectrum of the composite catalyst 1 manufactured in Example 1. The O 1s XPS spectrum of the catalyst is a spectrum deconvoluted 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 hydroxy peak (532.9 to 533.5 eV) derived from hydroxy radicals, and the spectrum was deconvoluted by fitting with a Gaussian function. In the O 1s XPS spectra of the catalysts manufactured in the examples and comparative examples, the ratio of the sum of the area of ​​the hydroxy peak (O3) and the area of ​​the adsorbed oxygen peak (O2) divided by the area of ​​the lattice oxygen peak (O1) ([O2+ O3] / O1×100, %) is 45 to 85%, and the ratio of the area of ​​the hydroxy peak (O3) divided by the area of ​​the adsorbed oxygen peak (O2) (O3 / O2×100, %) is summarized in Table 3.

[0155] [O2+O3] / O1×100O3 / O2×100[O2+O3] / O1×100O3 / O2×100Composite catalyst 178%11%Composite catalyst 735%38%Composite catalyst 264%23%Composite catalyst 118%0%Composite catalyst 371%28%Composite catalyst 241%0%Composite catalyst 474%24%Composite catalyst 356%41%Composite catalyst 564%54%Composite catalyst 451%15%Composite catalyst 671%95%Composite catalyst 550%58%

[0156] Figure 7 is an O2-TPD profile of the composite catalyst 1 manufactured in Example 1. In the O2-TPD profiles of the catalysts manufactured in the Examples and Comparative Examples, the area fraction (A) of the area of ​​the integrated area of ​​the spectrum lower portion in the temperature range of 500-600°C in the total area of ​​the integrated area of ​​the O2-TPD profile measured in the temperature range of 40-850°C 500-600 ) and the area fraction occupied by the integrated area of ​​the lower part of the spectrum in the temperature range of 600-850℃ (A 600-850 ) are summarized in Table 4. At this time, [100 - A 500-600 - A 600-850] corresponds to the area fraction occupied by the integrated area of ​​the lower part of the spectrum in the temperature range of 40-500℃.

[0157] A 500-600 A 600-850 A 500-600 A 600-850 Composite catalyst 115%27%Composite catalyst 74%36%Composite catalyst 211%23%Composite catalyst 10%4%Composite catalyst 315%21%Composite catalyst 256%41%Composite catalyst 418%40%Composite catalyst 313%42%Composite catalyst 514%29%Composite catalyst 49%32%Composite catalyst 615%28%Composite catalyst 511%38%

[0158] Fig. 8 is an X-ray diffraction pattern of composite catalyst 1 manufactured in Example 1, and Fig. 9 is an X-ray diffraction pattern of comparative catalyst 4 manufactured in comparative example 4. As in the example of Fig. 8, no peak due to manganese or manganese oxide was detected in the X-ray diffraction pattern of the composite catalysts manufactured in Examples 1 to 7, but in the case of comparative catalyst 4, a peak due to manganese oxide was detected.

[0159] In all composite catalysts manufactured 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 manufactured in Examples 1 to 7, the maximum intensity I of the (101) plane diffraction peak (2θ 25.3°) of the anatase phase 101 The maximum intensity of the (110) plane diffraction peak (2θ 27.7°) of the rutile phase I 110 Intensity ratio I 101 / I 110 was in the range of 6.21 to 6.60, which is the intensity ratio (I) of the titanium oxide (comparative catalyst 1) used as a raw material. 101 / I 110 ) is a similar value to 6.71.

[0160] The maximum intensity I of the (101) plane diffraction peak (2θ 25.3°) of the anatase phase in the X-ray diffraction patterns of the composite catalysts manufactured in Examples 1 to 7 and the titanium oxide (comparative catalyst 1) used as a raw material 101The maximum intensity of the diffraction peak I on the Athanase (200) plane 200 Intensity ratio divided by (I 101 / I 200 ) are summarized in Table 5 below.

[0161] I 101 / I 200 I 101 / I 200 Composite catalyst 14.09 Composite catalyst 54.06 Composite catalyst 23.96 Composite catalyst 64.09 Composite catalyst 32.82 Composite catalyst 73.87 Composite catalyst 43.78 Comparative catalyst 14.18

[0162] The methyl mercaptan removal performance, formaldehyde removal performance, trimethylamine removal performance, and toluene removal performance of the catalysts manufactured in the examples and comparative examples are summarized in Tables 6, 7, 8, and 9. In the tables, RH=0% is a state without moisture (humidity), RH=70% is a state containing moisture (humidity) with a relative humidity of 70%, 5 minutes refers to the removal efficiency at 5 minutes after supplying the malodor-containing gas to the fixed-bed glass reactor, and 1 hour refers to the removal efficiency at 60 minutes after supplying the malodor-containing gas to the fixed-bed glass reactor.

[0163] Methyl mercaptan removal performanceHumidityRH=0%RH=0%RH=70%RH=70%Time5 minutes1 hour5 minutes1 hourComposite catalyst 1100%100%100%100%Composite catalyst 2100%100%98%98%Composite catalyst 3100%100%97%99%Composite catalyst 4100%100%99%98%Composite catalyst 595%93%94%93%Composite catalyst 694%90%94%90%Composite catalyst 7100%98%92%89%Composite catalyst 10%0%0%0%Composite catalyst 251%45%31%8%Composite catalyst 382%76%77%43%Composite catalyst 483%78%75%42%Comparative catalyst 575%64%72%49%

[0164] Formaldehyde removal performanceHumidityRH=0%RH=0%RH=70%RH=70%Time5 minutes1 hour5 minutes1 hourComposite catalyst 1100%100%100%100%Composite catalyst 2100%100%96%92%Composite catalyst 3100%100%96%94%Composite catalyst 4100%100%100%99%Composite catalyst 596%95%92%92%Composite catalyst 694%93%88%85%Composite catalyst 790%83%84%82%Composite catalyst 10%0%0%0%Composite catalyst 263%55%51%22%Composite catalyst 372%64%78%42%Composite catalyst 475%71%67%61%Comparative catalyst 566%54%64%36%

[0165] Trimethylamine removal performanceHumidityRH=0%RH=0%RH=70%RH=70%Time5 minutes1 hour5 minutes1 hourComposite catalyst 1100%100%100%100%Composite catalyst 2100%100%100%100%Composite catalyst 3100%100%100%100%Composite catalyst 4100%100%99%99%Composite catalyst 591%88%89%88%Composite catalyst 689%82%80%79%Composite catalyst 792%83%75%73%Composite catalyst 10%0%0%0%Composite catalyst 256%50%32%11%Composite catalyst 377%68%75%48%Composite catalyst 473%65%60%41%Comparative catalyst 570%55%64%31%

[0166] Toluene Removal PerformanceHumidityRH=0%RH=0%RH=70%RH=70%Time5 minutes1 hour5 minutes1 hourComposite catalyst 1100%100%100%100%Composite catalyst 2100%100%100%100%Composite catalyst 3100%100%100%100%Composite catalyst 4100%100%100%100%Composite catalyst 5100%98%99%96%Composite catalyst 699%95%95%91%Composite catalyst 791%91%95%95%Composite catalyst 10%0%0%0%Composite catalyst 270%50%50%7%Composite catalyst 381%65%69%37%Composite catalyst 488%71%76%20%Comparative catalyst 580%58%71%42%

[0167] As described above, the present invention has been described through specific matters and limited embodiments and drawings, but these are provided only to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and those skilled in the art to which the present invention pertains can make various modifications and variations from this description. Therefore, the spirit of the present invention should not be limited to the described embodiments, and all things that are equivalent or equivalent to the following claims as well as the claims are considered to fall within the scope of the spirit of the present invention.

Claims

1. A titanium oxide composite catalyst containing a transition metal including manganese, The above composite catalyst contains on its surface at least one active oxygen species selected from the group consisting of surface-adsorbed oxygen and hydroxyl radicals, Absorbance at 500 nm wavelength in UV-Vis spectral spectrum (A 500 ) at a wavelength of 300 nm, the absorbance (A 300 ) divided by the ratio (A) 500 / A 300 ) is 0.85 or higher, A composite catalyst having a peak located in the temperature range of 240 to 275°C in a hydrogen temperature reduction profile.

2. In paragraph 1, A composite catalyst in which the second peak is located in the temperature range of 345 to 420°C in the above hydrogen temperature reduction profile.

3. In paragraph 1, In the X-ray photoelectron spectroscopy spectrum (XPS) of the above composite catalyst, it has 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. A composite catalyst wherein the ratio of the sum of the area of the hydroxy peak (O3) and the area of the adsorbed oxygen peak (O2) divided by the area of the lattice oxygen peak (O1) ([O2+ O3] / O1×100, %) is 45 to 85%, and the ratio of the area of the hydroxy peak (O3) divided by the area of the adsorbed oxygen peak (O2) (O3 / O2×100, %) is 50% or less.

4. In paragraph 1, In the oxygen temperature-elevated desorption profile of the above composite catalyst, the first area fraction (A) occupied by the area integrated under the oxygen temperature-elevated desorption profile in the temperature range of 500-600°C out of the total area integrated under the oxygen temperature-elevated desorption profile in the temperature range of 40-850°C 500-600 ) is 1 to 20%, and the second area fraction (A) occupied by the area integrated under the oxygen temperature increase desorption profile in the temperature range of 600-850℃ 600-850 ) is a composite catalyst of 20 to 40% 5. In any one of paragraphs 1 to 4, In the X-ray diffraction pattern of the above composite catalyst, the intensity I of the diffraction peak of the atanase (101) plane 101 The intensity of the diffraction peak I on the (110) side of the rutile 110 Intensity ratio divided by (I 101 / I 110 ) is a composite catalyst having 4 to 8 members.

6. In paragraph 5, In the X-ray diffraction pattern of the above composite catalyst, the intensity I of the diffraction peak of the atanase phase (101) plane 101 The intensity of the diffraction peak I on the Athanase (200) plane 200 Intensity ratio divided by (I 101 / I 200 ) is a composite catalyst with a value of 4.15 or less.

7. In paragraph 5, A composite catalyst which does not contain diffraction peaks due to manganese and manganese oxide in the above X-ray diffraction pattern.

8. In paragraph 1, A composite catalyst, wherein the manganese is contained in an amount of 1 to 15 wt% based on the total weight of the composite catalyst.

9. In paragraph 1, A composite catalyst comprising the above transition metal and manganese.

10. In paragraph 1, The above composite catalyst is a composite catalyst that is a catalyst for decomposing volatile organic compounds.

11. An odor gas remover comprising a composite catalyst according to paragraph 1. 12.S1) A step in which a first gas containing an odorous gas is supplied to a reaction space in which a composite catalyst according to paragraph 1 is located; S2) A step in which the odorous gas in the first gas comes into contact with the composite catalyst and the odorous gas is decomposed; and S3) A step in which the second gas generated by decomposition of the above odorous gas is discharged from the reaction space; A method for removing odorous gases including:

13. In paragraph 12, A method for removing a malodorous gas, wherein the malodorous gas is any one selected from the group consisting of an aldehyde compound, an aromatic hydrocarbon, an aliphatic hydrocarbon, an ammonia compound, and a mercaptan compound.

14. In paragraph 12, A method for removing an odorous gas, wherein the first gas contains moisture in the above step S1).

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