Deodorizing catalyst, as well as, producing method and purpose therefor

Abstract

To provide a deodorizing catalyst and a deodorizing product excellent in removing odor in a space such as within an automobile, in particular, odor due to acetaldehyde.SOLUTION: A deodorizing catalyst comprising a first metallic component and a transition metal oxide, wherein the first metallic component contains ruthenium and the content of ruthenium in the deodorizing catalyst is 0.1 to 10 mass%, and the transition metal oxide is at least one selected from the group consisting of cerium oxide and zirconium oxide, and in the X-ray diffraction pattern, in the region where 2θ is from 25° to 35°, there is the highest peak (α) in the region from 25° to less than 30°, and the peak intensity ratio (α / β) of the intensity of peak (α) to the intensity of the highest peak (β) in the region from 30° to less than 30.5° is 4 or more, and for deodorizing aldehydes, carboxylic acids, and sulfur compounds.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a deodorizing catalyst, and a method for producing the same and uses thereof. [Background technology]

[0002] Various odors generated in the environment (exhaust gas, garbage and food odors, odors emitted from newly constructed homes and buildings, etc.) are major social issues, and effective countermeasures are needed for each environment. Odors are particularly problematic in enclosed spaces such as homes, public facilities such as hotels and restaurants, and transportation facilities such as trains and automobiles. However, since people coexist in these spaces, installing specialized equipment (e.g., ozone deodorizers or hypochlorous acid deodorizers) is difficult and poses safety concerns. Therefore, easy-to-use adsorbents are preferred. However, continued use of adsorbents can exceed their adsorption capacity and cause breakthrough, requiring frequent replacement. Furthermore, particularly on hot days, odorous components that have been adsorbed can desorb from the adsorbent, resulting in the generation of unpleasant odors.

[0003] As a technology for adsorbing and decomposing odorous components in the air, photocatalysts and supported catalysts made by supporting precious metals on carriers such as silica are known to be effective in decomposing volatile organic compounds (VOCs) in the air.

[0004] For example, Patent Document 1 discloses a deodorizing catalyst in which a support is one or more metal oxides essentially containing ZrO2 or CeO2, and a specific metal such as Ag is supported on this support as a catalytic component. Patent Document 1 discloses several specific supported catalysts as such deodorizing catalysts, such as an Ag / CeO2 catalyst in which silver is supported on cerium oxide, an Rh / ZrO2 catalyst in which rhodium is supported on zirconium oxide, and a Pd / CeO2-SiO2 catalyst in which palladium is supported on a CeO2-SiO2 support, and also shows that these supported catalysts oxidatively decompose trimethylamine.

[0005] Patent Document 2 discloses a catalyst obtained by supporting a noble metal such as Pt on a composite oxide of cerium and zirconium, iron (III) oxide, or manganese dioxide, calcining the resulting mixture, and then subjecting the mixture to a reduction treatment using carbon monoxide to introduce oxygen vacancies. Patent Document 2 also discloses that the catalyst contains a certain amount or more of active oxygen that is active at 50°C or below, and is capable of removing carbon monoxide (CO), methyl mercaptan, triethylamine, and ethylene at room temperature.

[0006] Patent Document 3 also discloses a catalyst in which a precious metal such as Pt is supported on cerium oxide or a composite oxide of cerium and zirconium, the catalyst is calcined, and then reduced with carbon monoxide to introduce oxygen deficiencies. Patent Document 3 also shows that a small particle size of the precious metal in the catalyst results in high CO removal activity, and that the temperature at which the calcination is performed affects the particle size of the precious metal in the resulting catalyst.

[0007] Patent Document 4 discloses a Pt / zeolite catalyst obtained by hydrogen reduction of a mixture obtained by impregnating zeolite with a platinum compound, and also discloses that this Pt / zeolite catalyst can remove propionaldehyde, ethyl acetate, and trimethylamine. Patent Document 4 also shows that when the hydrogen reduction is carried out within a certain temperature range, the propionaldehyde removal performance of the resulting Pt / zeolite catalyst is improved.

[0008] Also, attempts have been made to develop deodorizing catalysts containing ruthenium. In this regard, Patent Document 5 discloses a catalyst obtained by treating a mixture of a cerium compound, a trace amount of a ruthenium compound, and a small amount of a third metal compound with an alkali, to obtain a catalyst precursor, which is then calcined in air. It also discloses that this catalyst is capable of removing propionaldehyde, ethyl acetate, acetaldehyde, and normal butyric acid. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Publication No. 10-296087 [Patent Document 2] Japanese Patent Application Laid-Open No. 2002-102700 [Patent Document 3] Japanese Patent Application Laid-Open No. 2002-102701 [Patent Document 4] International Publication No. 2022 / 071379 [Patent Document 5] International Publication No. 2022 / 118986 Summary of the Invention [Problem to be solved by the invention]

[0010] There are various substances that cause various odors in the environment, and acetaldehyde is one such substance. Acetaldehyde is a volatile organic compound (VOC) that causes odors in spaces such as automobile interiors, and is known to be one of the substances that cause sick building syndrome. Therefore, there is a strong demand for reducing odors caused by acetaldehyde, especially in the automotive field.

[0011] In this regard, various attempts have been made to use noble metal catalysts or supported catalysts containing noble metals as deodorizing catalysts.The present inventors have also found that, for example, platinum / zeolite-based deodorizing catalysts have a high deodorizing effect on odors caused by nitrogen-containing compounds such as trimethylamine and pyridine, and odors caused by specific aldehydes such as nonenal.However, even if conventional deodorizing catalysts have the ability to remove acetaldehyde, their performance generally tends to be insufficient.Therefore, conventional deodorizing catalysts have room for further improvement in their ability to remove acetaldehyde. Therefore, an object of the present invention is to provide a deodorizing catalyst and a deodorizing product that have excellent performance in removing odors, particularly odors caused by acetaldehyde, in spaces such as the interior of an automobile. [Means for solving the problem]

[0012] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that high deodorizing performance can be obtained when a catalyst having specific physical properties, which is formed by supporting ruthenium on a transition metal oxide, is used as a deodorizing catalyst, and have thus completed the present invention.

[0013] The present invention relates to, for example, the inventions described in the following [1] to

[15] . [1] A deodorizing catalyst comprising a first metal component and a transition metal oxide, the first metal component comprises ruthenium; the content of ruthenium in the deodorizing catalyst is 0.1 to 10 mass %, The transition metal oxide is at least one selected from the group consisting of cerium oxide and zirconium oxide, and In the X-ray diffraction pattern, in the 2θ region of 25 to 35°, the highest peak (α) is in the region of 25° or more and less than 30°, and the peak intensity ratio (α / β) of the intensity of the peak (α) to the intensity of the highest peak (β) in the region of 30° or more and less than 30.5° is 4 or more. Deodorizing catalyst for eliminating aldehydes, carboxylic acids, and sulfur compounds.

[0014] [2] The deodorizing catalyst according to [1], wherein the first metal component is supported on the transition metal oxide.

[0015] [3] The deodorizing catalyst according to [1] or [2], wherein the transition metal oxide is zirconium oxide.

[0016] [4] The deodorizing catalyst according to any one of [1] to [3], wherein the peak intensity ratio (α / β) is 4.5 or more.

[0017] [5] The deodorizing catalyst according to any one of [1] to [3], wherein the peak intensity ratio (α / β) is 4.9 or more.

[0018] [6] a step S1 of impregnating the transition metal oxide with a ruthenium compound; Step S2 of calcining the support obtained in step S1 at 350°C or higher; The deodorizing catalyst according to [1], which is produced by a production method comprising the steps of:

[0019] [7] a step S1 of impregnating the transition metal oxide with a ruthenium compound; Step S2 of calcining the support obtained in step S1 at 350°C or higher; A method for producing the deodorizing catalyst according to [1], comprising:

[0020] [8] The method according to [7], wherein the temperature at which the firing is carried out in step S2 is 400°C or higher.

[0021] [9] [7] The method according to [7], wherein the temperature at which the firing is carried out in step S2 is 500°C or higher.

[0022]

[10] The method according to any one of [7] to [9], wherein the ruthenium compound is a ruthenium halide.

[0023]

[11] The manufacturing method according to any one of [7] to

[10] , further comprising a step S3 of reducing the fired body obtained in the step S2.

[0024]

[12] A deodorant composition comprising the deodorizing catalyst according to any one of [1] to [6].

[0025]

[13] A deodorizing product comprising the deodorizing catalyst according to any one of [1] to [6] or the deodorizing composition according to

[12] .

[0026]

[14] The deodorizing product according to

[13] , which is a deodorizing fiber, a deodorizing paint, or a deodorizing sheet.

[0027]

[15]

[13] or

[14] .

[14] A chair upholstery, curtain, carpet, tile, wallpaper, air filter, or vehicle interior material, comprising the deodorizing product according to

[13] or

[14] . [Effects of the Invention]

[0028] According to the present invention, it is possible to provide a deodorizing catalyst and a deodorizing product having high deodorizing performance, particularly high acetaldehyde removal performance. [Brief explanation of the drawings]

[0029] [Figure 1] 1 shows XRD diffraction patterns of the deodorizing catalysts obtained in Examples and Comparative Examples. DETAILED DESCRIPTION OF THE INVENTION

[0030] The present invention will be described in detail below. [Deodorizing catalyst] The deodorizing catalyst according to the present invention contains a first metal component and a transition metal oxide.

[0031] First Metal Component The first metal component constituting the deodorizing catalyst of the present invention contains ruthenium. The ruthenium may be contained in a state in which its oxidation number is 0, or in a state in which its oxidation number is not 0 (e.g., +2, +3, or +4), or may have a composite form thereof. An example of ruthenium in an oxidation number of 0 is metallic ruthenium. Examples of ruthenium in an oxidation number other than 0 include ruthenium compounds such as oxides, halides, and oxyhalides. In other words, the first metal component contains metallic ruthenium, a ruthenium compound, or a combination thereof. Here, examples of ruthenium halides include ruthenium(III) chloride, ruthenium(III) bromide, and ruthenium(III) iodide.

[0032] The ruthenium content in the deodorizing catalyst according to the present invention is 0.1 to 10% by mass. Here, the ruthenium content is the ratio of the mass of ruthenium contained in the composition, converted into ruthenium atoms, to the total mass of the composition. From the viewpoint of (obtaining a sufficient deodorizing effect), the ruthenium content is preferably 0.3% by mass or more, more preferably 0.5% by mass or more. On the other hand, from the viewpoints of reducing raw material costs and improving metal dispersibility, the ruthenium content is preferably 5% by mass or less, more preferably 3% by mass or less.

[0033] Thus, the first metal component constituting the deodorizing catalyst of the present invention contains ruthenium. Here, in a typical and preferred embodiment of the present invention, the metal element constituting the first metal component is ruthenium alone. In this embodiment, the first metal component consists of metallic ruthenium, one or more ruthenium compounds containing no metal elements other than ruthenium, or a combination thereof. Here, "ruthenium alone" means that the metal element constituting the first metal component is essentially composed of ruthenium alone, and does not necessarily require that the first metal component does not contain even a single atom of a metal element other than ruthenium. That is, the first metal component may contain trace amounts of metal elements other than ruthenium that may be unavoidably contained due to the raw materials and manufacturing process of the deodorizing catalyst of the present invention.

[0034] However, in the present invention, the first metal component may further contain a metal other than ruthenium (hereinafter referred to as "other metal"), as long as the object of the present invention is not impaired. Examples of such other metals include Pt, Rh, Pd, Os, Ir, Cu, Al, Si, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, La, Sm, and Ce. The first metal component may contain only one of the "other metals" or may contain two or more of them. In the composition constituting the deodorizing catalyst of the present invention, the optional other metal may also be contained in a state in which its oxidation number is 0, or in a state in which its oxidation number is not 0, or may have a composite form thereof. When the first metal component constituting the deodorizing catalyst according to the present invention contains "other metals," the amount of the "other metals" is usually less than 100 mol%, preferably 50 mol% or less, more preferably 10 mol% or less, and even more preferably 1 mol% or less, based on 100 mol% of the amount of all metal atoms constituting the first metal component constituting the deodorizing catalyst. Here, when the first metal component contains two or more kinds of other metals, the total amount of the "other metals" is the amount mentioned above.

[0035] transition metal oxides In the present invention, the transition metal oxide constituting the deodorizing catalyst is at least one selected from the group consisting of cerium oxide and zirconium oxide, and preferably zirconium oxide. By using such an oxide as the transition metal oxide, the deodorizing catalyst of the present invention tends to have improved deodorizing performance against acetaldehyde, methyl mercaptan, etc.

[0036] In a typical embodiment of the present invention, the transition metal oxide functions as a carrier for supporting the first metal component. From the viewpoint of achieving both high deodorizing performance and easy handling of the powder, the average particle size of the transition metal oxide is usually 0.01 μm to 1000 μm, and preferably 0.1 μm to 100 μm. Here, in a typical embodiment of the present invention, the average particle size is the median diameter (the particle diameter at which the cumulative distribution value of particle diameters is 50% when the cumulative distribution is calculated; also called D50), which can be determined by measurement with a general laser diffraction particle size distribution analyzer or the like. Furthermore, from the viewpoint of high deodorizing performance, the specific surface area of the transition metal oxide is preferably 50 m 2 / g or more.

[0037] Deodorizing catalyst composition The deodorizing catalyst according to the present invention includes the first metal component and the transition metal oxide. In a typical embodiment of the present invention, the deodorizing catalyst according to the present invention has the first metal component supported on the transition metal oxide.

[0038] In a preferred embodiment of the present invention, the transition metal oxide is zirconium oxide. In this embodiment, the deodorizing catalyst of the present invention has, in its X-ray diffraction pattern, a highest peak (α) in the region of 2θ from 25° to 35° and less than 30°, and the peak intensity ratio (α / β) of the intensity of the peak (α) to the intensity of the highest peak (β) in the region of 30° to 30.5° is 4 or greater. The peak intensity ratio (α / β) is preferably 4.5 or greater, more preferably 4.9 or greater, even more preferably 5.0 or greater, and particularly preferably 5.4 or greater. A higher peak intensity ratio tends to improve deodorizing performance, and, for example, as shown in the Examples described below, tends to increase the deodorizing rate for acetaldehyde and methyl mercaptan. The inventors have confirmed that the peak intensity ratio also applies when the transition metal oxide is cerium oxide. The deodorizing catalyst according to the present invention can be suitably used as a deodorizing catalyst for deodorizing aldehydes, carboxylic acids, and sulfur compounds.

[0039] [Deodorizing catalyst manufacturing method] The deodorizing catalyst is not particularly limited in its production method as long as the object of the present invention is achieved. For example, a step S1 of impregnating the transition metal oxide with a ruthenium compound; Step S2 of calcining the support obtained in step S1 at 350°C or higher; It can be obtained by a production method including the steps of:

[0040] Process S1 Step S1 is a step of impregnating the transition metal oxide with a ruthenium compound. Specifically, this step S1 is Step S1-1: dissolving a ruthenium compound in a solvent to obtain a solution containing the ruthenium compound; Step S1-2: adding the transition metal oxide to the solution obtained in Step S1-1, and impregnating the transition metal oxide with the solution; Step S1-3: removing the solvent from the mixture obtained in Step S1-2 to isolate the supported material; Contains:

[0041] In a typical embodiment of the present invention, the ruthenium compound used in step S1-1 is a ruthenium salt, examples of which include ruthenium halides such as ruthenium chloride (III), ruthenium bromide (III), and ruthenium iodide (III), ruthenium nitrosyl nitrate, etc. In one exemplary and preferred embodiment of the present invention, the ruthenium compound is ruthenium chloride (III).

[0042] Examples of the solvent used in step S1-1 include water, ethanol, and other solvents that can dissolve the ruthenium compound and are easily removed in step S1-3. In a preferred exemplary embodiment of the present invention, the solvent is water. The amount of the solvent relative to the ruthenium compound is usually an amount that completely dissolves the entire amount of the ruthenium compound.

[0043] The "solution containing a ruthenium compound" obtained in step S1-1 may consist only of the ruthenium compound and the solvent, or may further contain, in addition to the ruthenium compound and the solvent, a compound of the "other metal" (hereinafter referred to as "compound of the other metal") described above in the section on the "first metal component." Examples of the "compound of the other metal" include chloroplatinic acid, rhodium chloride, palladium chloride, and iron chloride. When the "solution containing a ruthenium compound" contains the "compound of the other metal," the proportion of ruthenium atoms is preferably 10 to 99 mol% when the total of ruthenium atoms and atoms of the other metal contained in the "solution containing a ruthenium compound" is 100 mol%.

[0044] Step S1-2 is usually carried out in such a manner that the entire amount of the transition metal oxide is completely immersed in the solution obtained in step S1-1. Here, in step S1-2, the amount of the ruthenium compound varies depending on the type of the ruthenium compound, but is, for example, 0.1 to 10 mass% in terms of ruthenium atoms, where the total amount of the ruthenium compound, the transition metal oxide, and the optional "compound of another metal" is 100 mass%.

[0045] The removal in step S1-3 can be carried out by any method as long as it can remove the solvent from the mixture obtained in step S1-2, but can be carried out by, for example, vacuum distillation.

[0046] During step S1-2, or after step S1-2 and before step S1-3, a step of adding an alkaline solution to a mixture containing the ruthenium compound and the transition metal oxide to convert the ruthenium compound into the corresponding oxide or hydroxide, and thereby coprecipitating the oxide or hydroxide with the transition metal oxide, or precipitating the oxide or hydroxide on the transition metal oxide, may be carried out, if necessary.

[0047] A supported material that serves as a precursor of the deodorizing catalyst of the present invention is obtained by such step S1. In a typical embodiment of the present invention, the amount of ruthenium supported on the supported material obtained in step S1 is 0.1 to 10 mass %.

[0048] Process S2 Step S2 is a step of calcining the support obtained in step S1 at 350°C or higher. The temperature for the calcination is preferably 400°C or higher, more preferably 500°C or higher. The time for the calcination can be set appropriately, but is usually 30 minutes to 48 hours, preferably 3 to 24 hours, and more preferably 6 to 12 hours. The calcination may be carried out in air or in an inert gas atmosphere such as nitrogen, but is preferably carried out in air from the viewpoint of efficient dechlorination.

[0049] Generally, the longer the calcination time in step S2, the higher the peak intensity ratio (α / β) of the resulting deodorizing catalyst tends to be. However, depending on the type of ruthenium compound and the conditions (temperature, etc.) for the calcination, continuing the calcination for a certain period of time may not necessarily lead to a further improvement in the peak intensity ratio (α / β), and may even result in a slight decrease. In such cases, it is preferable to terminate the calcination without further continuing the calcination after a certain period of time. By carrying out the calcination, a calcined body is obtained from the support. After the calcination, in general, a step of cooling the obtained calcined body to room temperature is carried out.

[0050] Process S3 The above-mentioned production method includes the above-mentioned steps S1 and S2. Here, in the present invention, the sintered body obtained in step S2 may be used as a deodorizing catalyst as it is. However, from the viewpoint of higher deodorizing performance (particularly higher aldehyde deodorizing performance), it is preferable that the above-mentioned production method further includes, as step S3, a step of reducing the sintered body obtained in step S2. It is then preferable that the reduced sintered body obtained in step S3 be used as a deodorizing catalyst.

[0051] The reduction treatment can be carried out, for example, by a reduction method using a gaseous reducing agent such as hydrogen or carbon monoxide, or a reduction method using a liquid reducing agent such as ethanol, methanol, or hydrazine. Furthermore, depending on the type of sintered body obtained in step S2 and the conditions for the reduction treatment, this reduction treatment may also be carried out by a reduction method using a solid reducing agent such as sodium borohydride. In the present invention, the reduction treatment is preferably carried out by contacting the sintered body obtained in step S2 with hydrogen. The contact with hydrogen can be carried out by placing the sintered body under a flow of hydrogen gas or a mixed gas of hydrogen gas and an inert gas (e.g., nitrogen gas or argon gas). The temperature and time for the contact with hydrogen are not particularly limited as long as the object of the present invention is achieved, but for example, a temperature of 200 to 500°C for 1 to 24 hours is preferred.

[0052] [Deodorant composition] The deodorizing catalyst according to the present invention can be suitably used as a deodorizing catalyst for deodorizing aldehydes, carboxylic acids, and sulfur compounds.

[0053] The deodorizing catalyst according to the present invention may be used alone or in combination with components other than the deodorizing catalyst (hereinafter referred to as "other components"). That is, the deodorizing catalyst according to the present invention may be used in the form of a deodorizing composition containing the deodorizing catalyst, for example, a deodorizing composition containing the deodorizing catalyst and the "other components".

[0054] The "other components" include odor eliminating components that remove, neutralize or decompose odorous components, other than the deodorizing catalyst (hereinafter referred to as "other odor eliminating components"). Although known compounds can be used as the "other odor-removing component" without limitation, it is preferable to use a chemical adsorbent. In particular, by mixing a chemical adsorbent that exerts a deodorizing effect by chemically interacting with odorous substances with the deodorizing catalyst of the present invention, a deodorizer composition with improved initial performance can be obtained. That is, the "other odor-removing component" is preferably a chemical adsorbent, particularly a chemical adsorbent that exerts a deodorizing effect by chemically interacting with odorous substances. Examples of such chemical adsorbents include Toagosei's Kesmon NS-750 (organic amine-supported silica; for aldehydes), NS-70 (Ca, Mg-based compounds; for acids), NS-10 (zirconia phosphate; for ammonia), and NS-20C (Cu-based compound-supported silica; for sulfur compounds); Otsuka Chemical's Chemcatch (adipic acid dihydrazide; for aldehydes); and Sinase Zeomic's Dashlight S (amine compound-supported silica; for aldehydes).

[0055] Another example of the "other odor-removing component" that can be used in combination with the deodorizing catalyst is an odor-decomposing deodorizer. Examples of odor-decomposing deodorizers include catalysts carrying precious metals such as Pt and Pd, catalysts that utilize oxidation-reduction such as Fe, and photocatalysts such as titanium oxide.

[0056] The amount of the "other odor-eliminating components" that can be contained in the deodorant composition can be set appropriately depending on the specific application, and the total amount thereof is, for example, 1 to 90% by mass, with the entire deodorant composition being 100% by mass. The deodorant composition of the present invention can be suitably used in applications where deodorization or elimination of odors is required.

[0057] [Deodorizing products (deodorizers)] The deodorizing catalyst and deodorizing composition according to the present invention can be used in various deodorizing products (deodorizers) for industrial and household use. That is, the deodorizing product (deodorizer) of the present invention contains the deodorizing catalyst or the deodorizing composition.

[0058] Here, the deodorizing catalyst and deodorizer composition according to the present invention can be in the form of a liquid agent (liquid deodorizer), a solid agent (solid deodorizer), a gel-like solid agent (solid gel deodorizer), etc., and such liquid agents, solid agents, and gel-like solid agents can be appropriately prepared by known methods.

[0059] Examples of liquid deodorants include those prepared by dissolving the deodorant catalyst of the present invention or the deodorant composition of the present invention in an appropriate organic solvent such as water or ethanol, or emulsifying the same with an appropriate surfactant, or aerosol deodorants prepared by filling these liquids into a spray container together with a propellant. Examples of solid deodorants include powders prepared by mixing the deodorant catalyst of the present invention or the deodorant composition of the present invention with a powdered inorganic substance such as silica or perlite, those adsorbed on paper or a porous substance, or those kneaded into a synthetic resin such as polyethylene. Examples of solid gel deodorants include those prepared by adding the deodorant catalyst of the present invention or the deodorant composition of the present invention to a natural or synthetic polymer gel base such as agar, carrageenan, or polyethylene glycol. If necessary, surfactants, disinfectants, fragrances, colorants, etc. may be added to these formulations as appropriate.

[0060] The deodorizer of the present invention can be used for home use to deodorize rooms, refrigerators, toilets, trash cans, etc., and to remove and prevent body odor, and can also be used industrially to remove odors in sewage treatment plants, fish processing plants, fish meal manufacturing plants, livestock barns, livestock or poultry manure drying plants, pulp factories, etc.

[0061] Specific forms of deodorizing products containing the deodorizing catalyst of the present invention and deodorizing products containing the deodorizing composition of the present invention include various products such as deodorizing fibers, deodorizing paints, and deodorizing sheets. One useful deodorizing product using the deodorizing catalyst and deodorizer composition of the present invention is a deodorizing fiber. In this case, the deodorizing fiber (1) can be formed by attaching or bonding the deodorizing catalyst and deodorizer composition to the surface of raw fiber, or the deodorizing fiber (2) can be formed by embedding the deodorizing catalyst and deodorizer composition in the raw fiber so that they are exposed to the surface. The raw fiber can be either a natural fiber or a synthetic fiber, and can also be any of short fiber, long fiber, and composite fiber with a core-sheath structure.

[0062] The deodorizing fiber (1) can be obtained by applying a deodorizing agent-containing liquid composition (coating liquid) consisting of an aqueous or organic solvent-based suspension containing the deodorizing agent composition to the surface of the raw fiber by a method such as gravure coating, dipping, or spray coating, and then removing the medium such as the solvent.

[0063] This deodorant-containing liquid composition (coating liquid) may contain a binder to improve the adhesion of the deodorant composition to the surface of the raw fiber. Examples of binders include acrylic binders, acrylic silicone binders, styrene binders, and acrylic styrene binders. The ratio of deodorant to binder (deodorant / binder) is usually 95 / 5 to 10 / 90, preferably 90 / 10 to 30 / 70, and more preferably 80 / 20 to 40 / 60, and an appropriate ratio can be selected depending on the application. The lower the binder ratio, the more easily the deodorant's performance is achieved, but it tends to fall off the fiber more easily.

[0064] If the viscosity of the deodorant-containing liquid composition is low and the deodorant settles, a thickener can be added. Examples of thickeners include polysaccharides such as sodium alginate, methyl cellulose, hydroxypropyl cellulose, and xanthan gum, polyvinyl alcohol, and polymethacrylic acid-based thickeners. The amount of thickener added to the coating liquid is 0.01 to 10%, preferably 0.1 to 5%, and more preferably 0.2 to 2%. If the coating liquid's wettability to fibers is insufficient, a surfactant may be added. Examples of surfactants include sodium alkylbenzenesulfonate, sodium alkyloxybenzenesulfonate, sodium alkyl sulfates such as sodium lauryl sulfate, and acetylene glycol-based surfactants. The amount of surfactant added to the coating liquid is 0.01 to 10%, preferably 0.1 to 5%, and more preferably 0.2 to 2%. The pH of the aqueous coating liquid containing the deodorant composition is not particularly limited, but to fully utilize the performance of the deodorant composition, a pH of approximately 6 to 8 is preferred.

[0065] In addition, deodorizing fiber (2) can be obtained by blending the deodorizing composition of the present invention with a melt or dissolved fiber resin solution of a liquid fiber resin and then fiberizing the resulting deodorizing agent-containing resin composition. The fiber resin that can be used in this method is not particularly limited, and known chemical fibers can be used. Preferred resins include polyester, polyamide, acrylic, polyethylene, polypropylene, polyvinyl, polyvinylidene, polyurethane, and polystyrene. These resins may be homopolymers or copolymers. In the case of copolymers, the polymerization ratio of the monomers is not particularly limited.

[0066] The proportion of the deodorizing catalyst and deodorizing composition contained in the deodorizer-containing resin composition is not particularly limited. Generally, increasing the content of the deodorizing catalyst and deodorizing composition can make the deodorizing effect more powerful and last for a long period of time, but even if they are contained in a certain amount or more, there may not be a significant difference in the deodorizing effect or the strength of the deodorizing fiber may decrease, so the content is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the resin for fibers.

[0067] Another major deodorizing product using the deodorizing catalyst and deodorizer composition of the present invention is a deodorizing paint, which often takes the form of a deodorizer-containing paint composition. When producing a deodorant-containing paint composition, the oils, fats, or resins that serve as the main components of the paint vehicle used are not particularly limited and may be any of natural vegetable oils, natural resins, semi-synthetic resins, and synthetic resins. Usable oils, fats, and resins include, for example, drying or semi-drying oils such as linseed oil, tung oil, and soybean oil, rosin, nitrocellulose, ethyl cellulose, cellulose butyrate, benzyl cellulose, novolac-type or resol-type phenolic resins, alkyd resins, aminoalkyd resins, acrylic resins, vinyl chloride resins, silicone resins, fluororesins, epoxy resins, urethane resins, saturated polyester resins, melamine resins, and polyvinylidene chloride resins. The deodorant-containing paint composition may be either thermoplastic or curable.

[0068] The proportion of the deodorizing catalyst and deodorizing composition of the present invention contained in the deodorizer-containing paint composition is not particularly limited. Generally, increasing the content of the deodorizing catalyst and deodorizing composition will make the deodorizing effect more powerful and last for a longer period of time, but even if the content exceeds a certain level, there may not be a significant difference in the deodorizing effect, or the painted surface may lose its gloss or crack. Therefore, the content of the deodorizing catalyst and deodorizing composition is preferably 0.1 to 20 mass%, more preferably 0.5 to 10 mass%, relative to 100 mass% of the composition.

[0069] The deodorizing catalyst and deodorizing composition of the present invention can be used in both liquid and powder paints. The deodorizing agent-containing coating composition may be of a type that forms a film by any mechanism, and when the coating is cured, it may be of an oxidative polymerization type, moisture polymerization type, heat curing type, catalyst curing type, ultraviolet curing type, polyol curing type, or the like. It may also be applied to sintered coating, which is cured by baking. The pigments, dispersants, and other additives incorporated into the composition are not particularly limited, except for those that may chemically react with the deodorizing catalyst and deodorizing composition of the present invention. The deodorizing agent-containing coating composition can be easily prepared by thoroughly dispersing and mixing the raw material components using a common mixing device such as a ball mill, roll mill, disperser (disperser mixer), or mixer.

[0070] Another deodorizing product using the deodorizing catalyst and deodorizer composition of the present invention is a deodorizing sheet (including a deodorizing film). The raw material sheet before processing is not particularly limited, and its material, microstructure, etc. can be selected according to the intended use. Preferred materials for the raw material sheet include organic materials such as resin and paper, inorganic materials, or composites thereof. Raw material sheets that are breathable from one side to the other are preferably used. Other preferred examples of raw material sheets include Japanese paper, synthetic paper, nonwoven fabric, and resin film. Particularly preferred raw material sheets are paper made of natural pulp and / or synthetic pulp. When natural pulp is used as the raw material sheet, deodorizer particles tend to be sandwiched between the finely branched fibers. Therefore, natural pulp can sufficiently support the deodorizing catalyst or deodorizer composition of the present invention without the use of a binder, making it a practical support. On the other hand, synthetic pulp has the advantage of excellent chemical resistance. When synthetic pulp is used, it may be difficult to support the deodorizer particles due to the powder being sandwiched between the fibers. To prevent this, in the synthetic pulp manufacturing process, some of the fibers may be melted in the drying step after papermaking to increase the adhesive force between the powder and the fibers, or other thermosetting resin fibers may be mixed in with some of the fibers. By mixing natural pulp and synthetic pulp in an appropriate ratio, paper with various adjusted properties can be obtained, and generally, increasing the proportion of synthetic pulp makes it possible to obtain paper with excellent strength, water resistance, chemical resistance, oil resistance, etc., while increasing the proportion of natural pulp makes it possible to obtain paper with excellent water absorbency, gas permeability, hydrophilicity, moldability, texture, etc.

[0071] In the deodorizing sheet, the deodorizing composition may be contained throughout the entire raw material sheet from one side to the other side, may be disposed in a surface layer on one side or the other side, or may be disposed inside the raw material sheet excluding the surface layer.

[0072] The amount of the deodorizing catalyst and deodorant composition of the present invention carried in the deodorizing sheet is not particularly limited. Generally, increasing the amount of the deodorizing catalyst and deodorant composition carried will make the deodorizing effect more powerful and last for a longer period of time, but even if the amount is carried beyond a certain level, there will be no significant difference in the deodorizing effect. Therefore, the amount of the deodorizing catalyst and deodorant composition carried is preferably 0.1 to 10 parts by mass per 100 parts by mass of the raw material sheet.

[0073] The method for producing the deodorizing sheet is not particularly limited. The deodorizing catalyst and deodorant composition of the present invention may be supported either simultaneously with or after the production of the raw material sheet. For example, when supporting them on paper, a method of introducing the deodorizing catalyst and deodorant composition in any step of the papermaking process, or a method of applying, immersing, or spraying a deodorant-containing liquid composition (coating liquid) containing a binder onto pre-produced paper can be applied. The type of binder, thickener, and surfactant that can be added to the coating liquid are the same as those explained in the section on deodorizing fibers. When a deodorant-containing liquid composition is used, the amount of the deodorizing catalyst and deodorant composition supported is 0.05 to 10 g / m 2 It is preferable to coat the film so that the thickness is approximately equal to the thickness of the film.

[0074] [Application] The inventors speculate as follows about the deodorizing effect of the deodorizing catalyst of the present invention. The deodorizing catalyst of the present invention quickly reduces odorous substances in the surrounding gas by adsorbing them into the pores of the transition metal oxide, and decomposes at least a portion of the adsorbed odorous substances by the first metal component containing ruthenium supported on the transition metal oxide. Therefore, even when the deodorizing catalyst of the present invention is exposed to high temperatures after adsorbing odorous substances, it is less likely to release the odorous substances and diffuse the odor. Furthermore, because the adsorbed odorous substances are decomposed and diffused, the adsorption ability is not significantly reduced, and the catalyst can be used for deodorization for a long period of time.

[0075] In this way, the deodorizing catalyst of the present invention and the deodorizing composition and deodorizing product containing the same can reduce or eliminate odors over a long period of time by adsorbing and decomposing surrounding odorous substances, and in particular can reduce or eliminate odors caused by odorous substances selected from aldehydes such as acetaldehyde, carboxylic acids, and sulfur compounds such as thiols.

[0076] The deodorizing catalyst of the present invention and the deodorizing composition containing the same can be suitably used to reduce or eliminate odors caused by odorous substances in the atmosphere, and can be particularly suitably used to deodorize indoor spaces such as the inside of an automobile.

[0077] Furthermore, the deodorizing catalyst, deodorizing composition, and deodorizing product of the present invention can be applied to various uses without particular limitation, and can be applied to, for example, upholstery, curtains, carpets, tiles, wallpaper, air filters, and vehicle interior materials. In other words, these upholstery, curtains, carpets, tiles, wallpaper, air filters, and vehicle interior materials can also be said to include the deodorizing product of the present invention. Any form of the deodorizing product described above may be used for these uses.

[0078] Vehicles to which the vehicle interiors are applied include automobiles, trains, passenger planes, and ships. Examples of vehicle interior materials include ceiling materials, inner panels, door trims, headrests, steering wheels, shift levers, instrument panels, seat covers, floor materials, floor mats, and back door panels.

[0079] Other uses of the deodorizing product of the present invention include, in particular, the use of the deodorizing fiber in textile products such as clothing such as underwear, socks, and aprons, nursing clothing, futons, cushions, blankets, carpets, sofas, air filters, futon covers, curtains, and car seats, which are processed with deodorizing sheets.

[0080] As another application of the deodorizing product of the present invention, the deodorizing coating composition can be suitably used, for example, on the interior and exterior walls of buildings, vehicles, railways, etc., waste incineration facilities, food waste containers, etc. In particular, it can be used for building materials such as flooring and interior walls of factories with high VOC concentrations, and flooring and interior walls of fish markets. [Example]

[0081] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0082] [XRD measurement method] The X-ray diffraction (XRD) measurement of the deodorizing catalyst was carried out by a conventional method. The apparatus and measurement conditions used for the X-ray diffraction (XRD) measurement are as follows: X-ray diffraction measurement device: MiniFlex600-C (Rigaku Corporation) ·X-ray source: CuKα Output: 40kV, 15mA Divergence slit opening angle: 0.625° Scattering slit width: 13mm Receiving slit width: 13 mm 2θ: 20~50°

[0083] [Method for measuring the content of metals constituting the first metal component in a deodorizing catalyst or a calcined product] The content of the metal (such as ruthenium) constituting the first metal component in the deodorizing catalyst or the calcined body was measured by tableting the sample, attaching it to a sample holder, and performing X-ray fluorescence analysis under the following measurement conditions: ·Analysis method: Wavelength dispersive XRF Measurement device: ZSX Primus IV (Rigaku Corporation) ·X-ray tube: Rh Aperture: 10mmφ Measurement atmosphere: vacuum

[0084] [Examples 1 to 5, Comparative Examples 1 to 3] [Preparation of deodorizing catalyst A] In each of Examples 1 to 5 and Comparative Examples 1 and 2, deodorizing catalyst A was prepared as shown below.

[0085] 0.273 g of ruthenium(III) chloride n-hydrate (Fujifilm Wako Pure Chemical Industries, Ltd.) was weighed and dissolved in 80 mL of distilled water to obtain a solution. This solution was placed in a 300 mL eggplant-shaped flask, and 11 g of zirconium oxide (Daiichi Kigenso Kagaku Kogyo Co., Ltd., "RC-100 Zirconium Oxide," average particle size 2.6 μm) was then added to the same flask. The ruthenium compound solution was impregnated into the zirconium oxide to obtain a ruthenium loading of 1% by mass. The eggplant-shaped flask was then attached to a rotary evaporator, and the water was evaporated at 70 °C under vacuum. The remaining powder was then recovered. The recovered powder was placed in an electric furnace and calcined in air at the temperature and time shown in Table 1 (the "calcination step" in Table 1 refers to the calcination step). A calcined powder was obtained.

[0086] The ruthenium content in the obtained powdered sintered body was measured using the above-mentioned "Method for measuring the content of metals constituting the first metal component in a deodorizing catalyst or sintered body," and was found to be approximately 1.1 mass% for all of Examples 1 to 5 and Comparative Examples 1 to 3.

[0087] Next, in the examples and comparative examples other than Example 5, the powdery calcined body obtained by the calcination was reduced with hydrogen using a catalyst analyzer BELCAT-B (manufactured by Microtrack-Bell Corporation) as a heating furnace (in Table 1, "reduction step" refers to the step of performing the reduction). This catalyst analyzer includes an electric furnace, a cooling fan for cooling the electric furnace, and a gas port capable of supplying various gases.

[0088] First, the powdered calcined body was placed in a quartz tube, and the quartz tube was set in the electric furnace of the catalyst analyzer. Subsequently, the powdered calcined body was heated to 300°C at a rate of 10°C per minute under a 5% hydrogen / argon gas flow, and then maintained at 300°C for 2 hours. After that, the calcined body was cooled under a helium gas flow using the cooling fan attached to the catalyst analyzer (it took about 40 minutes to cool from 300°C to 40°C), thereby carrying out hydrogen reduction and preparing a reduced calcined body. The resulting reduced calcined body was designated deodorizing catalyst A.

[0089] The deodorizing catalysts A obtained in Examples 1 to 5 and Comparative Examples 1 to 2 were designated deodorizing catalysts A1 to A5 and AC1 to AC2, respectively. Although the ruthenium content of each of the resulting reduced and sintered bodies was not confirmed, the inventors experimentally performed XRF analysis on the sintered bodies and reduced and sintered bodies obtained in the same manner as in the Examples. They found that the chlorine content and ruthenium content were approximately equal in the sintered body before reduction, whereas the reduced and sintered body obtained by hydrogen reduction of the sintered body had a chlorine content of approximately 0.4% by mass, or about one-third, while the reduction in the ruthenium content tended to be only slight, at about 0.1% by mass. Considering this, along with the relatively low ruthenium content in the reduced and sintered body as a whole, the inventors estimated that the ruthenium content in each of the reduced and sintered bodies obtained in Examples 1 to 5 and Comparative Examples 1 to 2 was approximately 1.1% by mass, the same as that of the powdered sintered body.

[0090] For each of the deodorizing catalysts A obtained in Examples 1 to 5 and Comparative Examples 1 and 2 (i.e., deodorizing catalysts A1 to A5 and AC1 to AC2), X-ray diffraction (XRD) measurements were carried out using the apparatus and measurement conditions described in the above "XRD measurement method." The X-ray diffraction patterns of the deodorizing catalysts A obtained in Examples 1 to 5 and Comparative Examples 1 and 2 are summarized in Figure 1.

[0091] In the X-ray diffraction pattern, the highest peak among the peaks in the region of 25° or more and less than 30° was designated as peak (α), and the highest peak among the peaks in the region of 30° or more and less than 30.5° was designated as peak (β), and the ratio of the intensity of peak (α) to the intensity of peak (β) was calculated as the peak intensity ratio (α / β). The peak intensity ratios (α / β) calculated for each of the deodorizing catalysts A obtained in Examples 1 to 5 and Comparative Examples 1 and 2 (i.e., deodorizing catalysts A1 to A5 and AC1 to AC2) are shown in Table 1.

[0092] [Table 1]

[0093] As shown in FIG. 1, both the deodorizing catalysts A obtained in Examples 1 to 5 and the deodorizing catalysts A obtained in Comparative Examples 1 and 2 have the highest peak (α) in the region of 2θ between 25° and 30° in the region of 25 to 35° in the X-ray diffraction pattern.

[0094] Comparing Examples 1 to 4 with Comparative Examples 1 and 2, Examples 1 to 4 tend to have a larger peak intensity ratio (α / β) in the deodorizing catalyst A than Comparative Examples 1 and 2, in which the temperature for the calcination step is lower. Furthermore, from the results shown in Table 1 above for Examples 1 to 4, it can be seen that, if the temperature for the calcination step is the same, the longer the time for which the calcination step is performed, the larger the peak intensity ratio (α / β) in the resulting deodorizing catalyst A tends to be.

[0095] Looking at the results of Examples 1 to 4, there is an overall tendency for the peak intensity ratio (α / β) to increase with increasing calcination time (Examples 1, 3, and 4). Considering that heating ruthenium(III) chloride in air results in the decomposition and oxidation reaction to produce RuO2, we speculate that the ratio of RuO2 produced during the calcination process to unreacted ruthenium(III) chloride n-hydrate or some intermediate that may be produced during the conversion of ruthenium(III) chloride n-hydrate to RuO2 may be related to the peak intensity ratio (α / β) in the final deodorizing catalyst. However, when the calcination time is extended beyond a certain point, the increase in the peak intensity ratio (α / β) plateaus, and in Example 2, despite the calcination time being longer than in Example 1, the peak intensity ratio (α / β) slightly decreased. The reason for this decrease in the peak intensity ratio (α / β) is unknown, but it is speculated that the RuO2 production reaction during the calcination process is likely to be largely completed within a certain period of time, and that the RuO2 that was produced is then gradually consumed and reduced by some further reaction (for example, the production of volatile RuO4), which may lead to a decrease in the peak intensity ratio (α / β) in the final deodorizing catalyst.

[0096] Furthermore, when Example 1 and Example 5 are compared, even though the conditions for carrying out the calcination step are the same, Example 5, which did not carry out the reduction step, tends to have a slightly smaller peak intensity ratio (α / β) in the deodorizing catalyst A than Example 1, which was carried out in the same manner except for the reduction step. Nevertheless, Example 5 tends to have a similar peak intensity ratio (α / β) when compared with other Examples (e.g., Examples 2 and 3).

[0097] [Deodorizing evaluation] The deodorizing catalysts A obtained in each of the Examples and Comparative Examples were evaluated for deodorizing ability as shown below.

[0098] 10 mg of the deodorizing catalyst A prepared above was weighed out, wrapped in nylon mesh (manufactured by AS ONE Corporation, mesh size: 10 μm), and placed in a 5 L sampling bag (manufactured by Omi Odor Air Service Co., Ltd., material: vinyl alcohol polymer film). A sampling bag without deodorizing catalyst A was used as a blank.

[0099] Three liters of air that had been filtered through an activated carbon filter was introduced into the sampling bag, and then an aqueous solution of odor components was poured into the sampling bag so that the odor components in the sampling bag reached the specified concentrations (propionaldehyde: 8 ppm, methyl mercaptan: 8 ppm). After leaving the bag to stand at room temperature for 27 hours, the concentration of each odor component was measured, and the deodorization rate was calculated using the following formula. The odor component concentrations were measured using gas detector tubes (acetaldehyde detection tube "133SC Acetaldehyde" (manufactured by Komyo Rikagaku Kogyo Co., Ltd.) for detecting acetaldehyde, and mercaptans detector tube "130U Mercaptans" (manufactured by Komyo Rikagaku Kogyo Co., Ltd.) for detecting methyl mercaptan). Deodorization rate (%)=(XY) / X X: Odor component concentration in the blank sampling bag Y: Odor component concentration in the sampling bag containing deodorizing catalyst A The results are shown in Table 2.

[0100] [Table 2]

[0101] Tables 1 and 2 show that catalysts with a high peak intensity ratio (α / β) have a high deodorizing rate for acetaldehyde and methyl mercaptan.

Claims

1. A deodorizing catalyst comprising a first metal component and a transition metal oxide, the first metal component comprises ruthenium; the content of ruthenium in the deodorizing catalyst is 0.1 to 10 mass %, The transition metal oxide is at least one selected from the group consisting of cerium oxide and zirconium oxide, and In the X-ray diffraction pattern, in the 2θ region of 25 to 35°, the highest peak (α) is in the region of 25° or more and less than 30°, and the peak intensity ratio (α / β) of the intensity of the peak (α) to the intensity of the highest peak (β) in the region of 30° or more and less than 30.5° is 4 or more. Deodorizing catalyst for eliminating aldehydes, carboxylic acids, and sulfur compounds.

2. 2. The deodorizing catalyst according to claim 1, wherein the first metal component is supported on the transition metal oxide.

3. 2. The deodorizing catalyst according to claim 1, wherein the transition metal oxide is zirconium oxide.

4. 2. The deodorizing catalyst according to claim 1, wherein the peak intensity ratio (α / β) is 4.5 or more.

5. 2. The deodorizing catalyst according to claim 1, wherein the peak intensity ratio (α / β) is 4.9 or more.

6. a step S1 of impregnating the transition metal oxide with a ruthenium compound; a step S2 of calcining the support obtained in the step S1 at 350°C or higher; The deodorizing catalyst according to claim 1, which is produced by a production method comprising the steps of:

7. a step S1 of impregnating the transition metal oxide with a ruthenium compound; a step S2 of calcining the support obtained in the step S1 at 350°C or higher; A method for producing the deodorizing catalyst according to claim 1, comprising:

8. The method according to claim 7 , wherein the firing temperature in step S2 is 400° C. or higher.

9. The method according to claim 7 , wherein the firing temperature in step S2 is 500° C. or higher.

10. The method according to claim 7, wherein the ruthenium compound is a ruthenium halide.

11. The method according to any one of claims 7 to 10, further comprising a step S3 of reducing the fired body obtained in the step S2.

12. A deodorizing composition comprising the deodorizing catalyst according to claim 1.

13. A deodorizing product comprising the deodorizing catalyst according to any one of claims 1 to 6 or the deodorizing composition according to claim 12.

14. 14. The deodorizing product according to claim 13, which is a deodorizing fiber, a deodorizing paint, or a deodorizing sheet.

15. 14. An upholstery, curtain, carpet, tile, wallpaper, air filter, or vehicle interior material comprising the odor eliminating product of claim 13.

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