JP2006217995A - Deodorant, method of manufacturing deodorant, and deodorizer using the deodrant - Google Patents

Deodorant, method of manufacturing deodorant, and deodorizer using the deodrant Download PDF

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JP2006217995A
JP2006217995A JP2005032541A JP2005032541A JP2006217995A JP 2006217995 A JP2006217995 A JP 2006217995A JP 2005032541 A JP2005032541 A JP 2005032541A JP 2005032541 A JP2005032541 A JP 2005032541A JP 2006217995 A JP2006217995 A JP 2006217995A
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adsorbent
odor
deodorizing
filter
metal
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JP4904695B2 (en
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Mitsuhiro Sano
光宏 佐野
Yoshifumi Moriya
好文 守屋
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

<P>PROBLEM TO BE SOLVED: To provide a deodorant capable of adsorbing and removing the odor generated in the living space by an adsorbent with the physical adsorption effect. <P>SOLUTION: The deodorant consists of at least the adsorbent (not indicated) with the adsorption effect, a metal 5 with the catalytic effect, and a carrier 3 carrying the adsorbent. The deodorant is characterized by the catalytic metal 5 which is adsorbed/removed by the adsorbent (not indicated) after converting the aldehydes to carboxylic acid. The deodorant which can adsorb/remove the odor generated in the living space by the adsorbent with the physical adsorption effect and which can adsorb/remove especially harmful acetaldehyde by converting acetaldehyde to acetic acid by a platinum catalyst at ordinary temperature can be provided. With this deodorant, a deodorizer which can be used without a user's labor and without maintenance can be provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、生活空間の気体に含まれる臭気物質を吸着除去でき、特にタバコの主成分で、VOCの一種でもある有害性の高いアセトアルデヒドを有害性の小さい酢酸へ転化し、それを吸着除去することができる脱臭体および脱臭体の製造方法およびそれを用いた脱臭装置に関するものである。   The present invention can adsorb and remove odorous substances contained in the gas of living space, and in particular converts a highly harmful acetaldehyde, which is a main component of tobacco and also a kind of VOC, into less harmful acetic acid and removes it by adsorption. The present invention relates to a deodorizing body, a method for producing the deodorizing body, and a deodorizing apparatus using the same.

従来、白金属を用いた触媒を高温(200℃以上)で作動させ、臭気物質などを水や二酸化炭素などへ分解する白金系の熱触媒が広く知られている。また、特開平10−180108号にはマンガンを主体とする遷移金属による複合酸化物を用いた脱臭用の触媒について開示されている。これによるとマンガンとコバルトの複合酸化物により、50℃でアセトアルデヒドを80%分解されるとしている(例えば、特許文献1参照)。   Conventionally, a platinum-based thermal catalyst that operates a catalyst using a white metal at a high temperature (200 ° C. or higher) and decomposes odorous substances into water, carbon dioxide, and the like is widely known. Japanese Patent Application Laid-Open No. 10-180108 discloses a deodorizing catalyst using a composite oxide of transition metal mainly composed of manganese. According to this, 80% of acetaldehyde is decomposed at 50 ° C. by a complex oxide of manganese and cobalt (see, for example, Patent Document 1).

さらには、常温での臭気の分解触媒として、比表面積が大きな担体に光触媒を担持した光触媒脱臭フィルターとして以下の発明がある(例えば、特許文献2、特許文献3参照)。
特開平10−180108号公報 特開平6−343875号公報 特開2003−53196号公報
Furthermore, there are the following inventions as photocatalyst deodorization filters in which a photocatalyst is supported on a carrier having a large specific surface area as an odor decomposition catalyst at room temperature (see, for example, Patent Document 2 and Patent Document 3).
Japanese Patent Laid-Open No. 10-180108 JP-A-6-343875 JP 2003-53196 A

しかしながら、従来の白金系の触媒や上記特許文献1に開示の脱臭体では作動温度が高く、エアコンや空気清浄機などに応用できないという課題があり、また光触媒は吸着剤などと比較して脱臭速度が遅いことや、光源が必要であるためサイズを小さくできない、コストが高い、耐衝撃性が弱いなどの課題を有していた。   However, the conventional platinum-based catalyst and the deodorizing body disclosed in Patent Document 1 have a problem that the operating temperature is high and cannot be applied to an air conditioner, an air cleaner, and the like. However, since the light source is necessary, the size cannot be reduced, the cost is high, and the impact resistance is weak.

本発明は、前記従来の課題を解決するもので、生活空間で発生する臭気を物理吸着作用を有する吸着剤により吸着除去できる脱臭体を提供することを目的とする。   An object of the present invention is to solve the above-described conventional problems, and to provide a deodorizing body capable of adsorbing and removing odor generated in a living space by an adsorbent having a physical adsorption action.

上記課題を解決するに本発明の脱臭体は、少なくとも吸着作用を有する吸着剤と触媒作用を有する金属と前記吸着剤を担持する担体とから構成され、前記金属がアルデヒド類をカルボン酸へ転化後、前記吸着剤で吸着除去することを特徴とするもので、生活空間で発生する臭気を物理吸着作用を有する吸着剤により吸着除去でき、特に有害なアセトアルデヒドを白金系の触媒により常温で酢酸へ転化し、吸着剤により吸着除去できる脱臭体を実現できる。   In order to solve the above problems, the deodorizer of the present invention comprises at least an adsorbent having an adsorbing action, a metal having a catalytic action, and a carrier supporting the adsorbent, and the metal converts aldehydes to carboxylic acids. It is characterized by adsorbing and removing with the above adsorbent, and it can absorb and remove odors generated in living space with an adsorbent having a physical adsorption action, and converts harmful acetaldehyde to acetic acid at room temperature with a platinum-based catalyst. Thus, a deodorizing body that can be adsorbed and removed by the adsorbent can be realized.

本発明によれば、生活空間で発生する臭気を吸着除去でき、特に有害なアセトアルデヒドを常温で有害性の小さい酢酸へと転化し、吸着除去できる脱臭体を提供することができる。また、本発明によれば、人の手を煩わすことなく、メンテナンスフリーで使用できる脱臭装置を提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, the deodorizing body which can adsorb and remove the odor which generate | occur | produces in a living space, can convert especially harmful acetaldehyde into acetic acid with little toxicity at normal temperature, and can adsorb and remove can be provided. Moreover, according to this invention, the deodorizing apparatus which can be used maintenance-free without bothering a human hand can be provided.

第1の発明は、少なくとも吸着作用を有する吸着剤と触媒作用を有する金属と前記吸着剤を担持する担体とから構成され、前記金属がアルデヒド類をカルボン酸へ転化後、前記吸着剤で吸着除去することを特徴とするもので、生活空間で発生する臭気を物理吸着作用を有する吸着剤により吸着除去でき、特に有害なアセトアルデヒドを白金系の触媒により常温で酢酸へ転化し、吸着剤により吸着除去できる脱臭体を実現できる。   The first invention is composed of at least an adsorbent having an adsorbing action, a metal having a catalytic action, and a carrier carrying the adsorbent, and the metal converts aldehydes to carboxylic acids and then adsorbs and removes with the adsorbent. The odor generated in the living space can be adsorbed and removed by an adsorbent with a physical adsorption action, especially harmful acetaldehyde is converted to acetic acid at room temperature by a platinum-based catalyst, and adsorbed and removed by an adsorbent. A deodorizing body that can be produced can be realized.

第2の発明は、吸着剤が疎水性ゼオライトであるもので、シリカ分を高めたゼオライトは極性が小さくなるため、非極性の臭気分子を吸着できるようになり、また雰囲気の湿度に依存することなく臭気分子を吸脱着できるようになるため、多様な臭気分子を吸着除去できる脱臭体を実現できる。   In the second invention, the adsorbent is a hydrophobic zeolite, and the zeolite with increased silica content has a small polarity, so that it can adsorb non-polar odor molecules and depends on the humidity of the atmosphere. Since odor molecules can be adsorbed and desorbed without any problems, it is possible to realize a deodorant that can adsorb and remove various odor molecules.

第3の発明は、担体が無機繊維から形成されるハニカム構造体であるもので、通気抵抗が小さく、比表面積が大きいため、圧損を抑え、臭気の吸脱着効率が高い脱臭体を実現できる。   The third invention is a honeycomb structure in which the carrier is formed of inorganic fibers, and since the ventilation resistance is small and the specific surface area is large, it is possible to realize a deodorizing body that suppresses pressure loss and has high odor absorption / desorption efficiency.

第4の発明は、金属が少なくとも吸着剤表面に担持されている構成としたもので、さらに触媒作用を有する金属の分散性を高め、比表面積を大きくすることができるため、触媒活性の高い脱臭体を実現できる。   In the fourth invention, the metal is supported at least on the surface of the adsorbent, and further, the dispersibility of the metal having a catalytic action can be increased and the specific surface area can be increased. The body can be realized.

第5の発明は、吸着剤はゼオライトを含み、前記吸着剤に吸着したカルボン酸が、通気により脱着されることで、前記吸着剤が再生される構成としたもので、吸脱着しやすい吸着剤であるゼオライトを担持した脱臭体に通気することにより、飽和吸着に達したゼオライトが脱着再生され、メンテナンスフリーで長期間使用できる脱臭体を実現できる。   In a fifth aspect of the present invention, the adsorbent contains zeolite, and the carboxylic acid adsorbed on the adsorbent is desorbed by aeration so that the adsorbent is regenerated. By passing the air through the deodorizing body supporting zeolite, the zeolite that has reached saturation adsorption is desorbed and regenerated, and a deodorizing body that can be used for a long time without maintenance is realized.

第6の発明は、担体へ、少なくとも吸着作用を有する吸着剤と親水性の金属酸化物とを担持した後、白金属の酸溶液に浸漬し、焼成により触媒作用を有する金属を前記金属酸化物へ担持するもので、白金等の酸溶液を用いて白金等を担持する場合、乾燥もしくは焼成時に溶液が蒸発しやすい担体の端へ集まり分散性が低下する課題があるが、予め親水性の金属酸化物を高分散させ担持しておくと金属酸化物へ酸溶液が集まりやすくなるため、白金等の比表面積を大きくすることができ、触媒活性の高い脱臭体を実現できる。   According to a sixth aspect of the present invention, at least an adsorbent having an adsorbing action and a hydrophilic metal oxide are supported on a carrier, and then immersed in an acid solution of a white metal, and the metal having a catalytic action is calcined by firing. In the case where platinum or the like is supported using an acid solution such as platinum, there is a problem that the solution tends to evaporate at the end of the carrier during drying or firing, and the dispersibility is lowered. When the oxide is highly dispersed and supported, the acid solution easily collects on the metal oxide, so that the specific surface area of platinum or the like can be increased, and a deodorant with high catalytic activity can be realized.

第7の発明は、金属酸化物に酸化チタンを含むもので、光触媒作用を有する酸化チタンは、表面に紫外光を照射することにより超親水性となるため、酸溶液が集まりやすくなり、白金等の比表面積を大きくすることができ、触媒活性の高い脱臭体を実現できる。   In the seventh invention, titanium oxide is included in the metal oxide, and titanium oxide having a photocatalytic action becomes superhydrophilic by irradiating the surface with ultraviolet light. The specific surface area can be increased, and a deodorant with high catalytic activity can be realized.

第8の発明は、少なくとも臭気を含む空気を導入する吸気口と、前記臭気を含む空気を吸気する吸気手段と、前記吸気手段により吸気した空気に含まれる臭気を脱臭するフィルターと、前記フィルターにより脱臭された空気を室内へ導入する導入口と、前記フィルターから脱着した臭気を室外へ排気する排気口とを備え、前記フィルターが請求項1〜5のいずれか1項に記載の脱臭体である脱臭装置で、吸着剤を担持した脱臭体に通気することにより、飽和吸着に達した吸着剤から脱着した臭気が室外に排気されることで、メンテナンスフリーで長期間使用できる脱臭装置を実現できる。   According to an eighth aspect of the present invention, there is provided an intake port for introducing air containing at least odor, an intake means for taking in air containing the odor, a filter for deodorizing odor contained in the air taken in by the intake means, and the filter. The deodorizer according to any one of claims 1 to 5, further comprising an introduction port for introducing deodorized air into the room and an exhaust port for exhausting the odor desorbed from the filter to the outside of the room. The deodorization device that can be used for a long time without maintenance is realized by ventilating the deodorizer carrying the adsorbent with the deodorizer and exhausting the odor desorbed from the adsorbent that has reached saturation adsorption to the outside of the room.

第9の発明は、少なくとも臭気を含む空気を導入する吸気口と、前記臭気を含む空気を吸気する吸気手段と、前記吸気手段により吸気した空気に含まれる臭気を脱臭するフィルターと、前記フィルターにより脱臭された空気を室内へ導入する導入口と、前記フィルターから脱着した臭気を室外へ排気する排気口とを備え、前記フィルターが請求項6または7記載の製造方法で製造した脱臭体である脱臭装置で、予め親水性の金属酸化物を高分散させ担持しておくと金属酸化物へ酸溶液が集まりやすくなるため、白金等の比表面積を大きくすることができ、触媒活性の高い脱臭体を有する脱臭装置を実現できる。   According to a ninth aspect of the present invention, there is provided an intake port for introducing air containing at least an odor, an intake means for taking in air containing the odor, a filter for deodorizing odor contained in the air taken in by the intake means, and the filter. A deodorizing device comprising an inlet for introducing deodorized air into the room and an exhaust port for exhausting the odor desorbed from the filter to the outside, wherein the filter is a deodorant produced by the production method according to claim 6 or 7. If the device is preliminarily dispersed and supported with a hydrophilic metal oxide, the acid solution easily collects on the metal oxide, so that the specific surface area of platinum or the like can be increased, and a deodorant with high catalytic activity can be obtained. The deodorizing apparatus which has can be implement | achieved.

以下、本発明の実施の形態について、図面を参照しながら説明する。なお、この実施の形態によって本発明が限定されるものではない。   Hereinafter, embodiments of the present invention will be described with reference to the drawings. Note that the present invention is not limited to the embodiments.

(実施の形態1)
図1(a)は本発明の第1の実施の形態における脱臭体を示す外観模式図であり、(b)は脱臭体表面の拡大模式図である。脱臭体1は、シリカやアルミナなどの無機繊維で構成される平板および波形板を交互に積層されたハニカム構造体であり、通気方向2へ低い通気抵抗で通気することができる。
(Embodiment 1)
Fig.1 (a) is an external appearance schematic diagram which shows the deodorizing body in the 1st Embodiment of this invention, (b) is an enlarged schematic diagram of the deodorizing body surface. The deodorizing body 1 is a honeycomb structure in which flat plates and corrugated plates made of inorganic fibers such as silica and alumina are alternately stacked, and can be ventilated in the ventilation direction 2 with low ventilation resistance.

無機繊維で構成された平板および波形板は担体3となり、物理吸着作用を有する吸着剤4(以下、本実施の形態では物理吸着剤4という)および触媒作用を有する金属5(以下、本実施の形態では触媒金属5という)を繊維表面に担持する。   A flat plate and a corrugated plate made of inorganic fibers become a carrier 3, and an adsorbent 4 having a physical adsorption action (hereinafter referred to as a physical adsorbent 4 in the present embodiment) and a metal 5 having a catalytic action (hereinafter referred to as the present embodiment). In the form, the catalyst metal 5 is supported on the fiber surface.

物理吸着剤4や触媒金属5を担体3にアンカー効果もしくは物理的な結合もしくは化学的な結合などの作用により結合させ、担持されている。このときバインダを添加し、前記効果を高めると良いが、添加量が多い場合、吸着効果や触媒活性を低下させる原因となり、少ない場合、担体3との密着力が低下し、剥がれ落ちやすくなる。望ましくは、物理吸着剤4とバインダとの固形分が重量比で1:1〜20:1程度である。また、バインダは無機系のものが望ましく、コロイダルシリカや水ガラス、リン酸アルミニウムなどが適している。   The physical adsorbent 4 and the catalytic metal 5 are supported and supported on the support 3 by an action such as an anchor effect or a physical bond or a chemical bond. At this time, it is preferable to add a binder to enhance the effect. However, if the addition amount is large, it may cause a decrease in the adsorption effect and catalytic activity, and if it is small, the adhesion with the carrier 3 is lowered and the film is easily peeled off. Desirably, the solid content of the physical adsorbent 4 and the binder is about 1: 1 to 20: 1 by weight ratio. The binder is preferably inorganic, and colloidal silica, water glass, aluminum phosphate, and the like are suitable.

物理吸着剤4は、ゼオライト、シリカゲル、セピオライト、アルミナ、活性炭等の物理吸着作用を有する物質が用いられるが、製造上、触媒焼成のために400℃以上に昇温することや吸脱着のし易さを考慮すると、ゼオライトが最も望ましく、特にシリカ/アルミナ比が大きいため極性が小さい疎水性ゼオライトを用いるとよい。これにより、非極性の臭気分子も吸着するようになり、また雰囲気の湿度に依存することなく臭気分子を吸脱着できるため、多様な臭気分子を吸脱着できる脱臭体を実現できる。   As the physical adsorbent 4, a substance having a physical adsorption action such as zeolite, silica gel, sepiolite, alumina, activated carbon or the like is used. However, in production, it is easy to raise the temperature to 400 ° C. or higher for adsorption and desorption. In view of this, zeolite is most desirable, and a hydrophobic zeolite having a low polarity due to a large silica / alumina ratio is particularly preferable. As a result, non-polar odor molecules can be adsorbed, and the odor molecules can be adsorbed and desorbed without depending on the humidity of the atmosphere, so that a deodorant capable of adsorbing and desorbing various odor molecules can be realized.

また、本実施の形態で用いた疎水性ゼオライトは0.1〜10μm程度の径であるが、この大きさに限定されるものではない。しかしながら、大きさを小さくした方が、同体積での表面積を大きくとることができるので好ましい。さらに、疎水性ゼオライトの形は図中にあるような球状に限定されるものではなく、また実際は物理吸着剤の一次粒子が集まり、二次粒子を形成したり、さらには三次粒子を形成したりした粒子が担体3へ担持されていると考えられる。脱臭体の表面に凹凸を設けることにより、単位体積あたりの表面積を増やすことができるようになり、より効果的である。   Further, the hydrophobic zeolite used in the present embodiment has a diameter of about 0.1 to 10 μm, but is not limited to this size. However, it is preferable to reduce the size because the surface area can be increased with the same volume. Furthermore, the shape of the hydrophobic zeolite is not limited to the spherical shape as shown in the figure, and actually, the primary particles of the physical adsorbent gather to form secondary particles, or even tertiary particles. It is considered that the particles thus carried are supported on the carrier 3. By providing irregularities on the surface of the deodorizing body, the surface area per unit volume can be increased, which is more effective.

本実施の形態では、脱臭体1に無機繊維で構成される平板および波形板を交互に積層されたハニカム構造体を用いたが、物理吸着剤4を格子状に押出成型を行ったハニカム構造体を用いても良い。これにより、バインダを用いることがなくハニカム構造体全体を物理吸着剤4とすることができるので、吸着効果が高い脱臭体を実現できる。   In the present embodiment, a honeycomb structure in which flat plates and corrugated plates made of inorganic fibers are alternately laminated on the deodorizing body 1 is used. However, a honeycomb structure in which the physical adsorbent 4 is extruded in a lattice shape. May be used. Thereby, since the whole honeycomb structure can be made into the physical adsorbent 4 without using a binder, the deodorizing body with a high adsorption effect is realizable.

触媒金属5は、白金属に属し触媒作用を有する元素でルテニウム、ロジウム、パラジウム、オスミウム、イリジウム、白金が挙げられ、特に扱いやすさや入手のしやすさ、触媒活性などの理由で、白金、パラジウム、ロジウム、ルテニウムを用いることが望ましい。また触媒金属5もアンカー効果もしくは物理的な結合もしくは化学的な結合などの作用により、担体3あるいは物理吸着剤4に担持されている。   The catalytic metal 5 is an element belonging to a white metal and having catalytic action, and examples thereof include ruthenium, rhodium, palladium, osmium, iridium, and platinum, and platinum, palladium, and the like are particularly easy to handle, easily available, and have catalytic activity. It is desirable to use rhodium, ruthenium. Further, the catalytic metal 5 is also supported on the carrier 3 or the physical adsorbent 4 by an action such as an anchor effect or a physical bond or a chemical bond.

次に担持方法について説明する。物理吸着剤4の担体3への担持方法については、スプレーなどを用いた噴霧法、ディップ法などあるが、物理吸着剤4と必要に応じてバインダを水や溶剤などに分散もしくは溶解させ、ハニカム構造体をそのスラリーあるいは溶液に浸漬することで担持するディップ法が望ましい。また、粉末状の物理吸着剤4を分散させ、スラリーを作製する場合、物理吸着剤4の平均径は小さい方が望ましく、一次粒子の平均径で1μm以下程度が望ましい。さらには、なるべく凝集が起こらないように水や溶媒に分散させることが望ましく、必要に応じて分散剤を添加すると良い。   Next, the carrying method will be described. The method for supporting the physical adsorbent 4 on the carrier 3 includes a spraying method using a spray and the dip method. The physical adsorbent 4 and, if necessary, a binder are dispersed or dissolved in water, a solvent, etc. A dip method for supporting the structure by immersing the structure in the slurry or solution is desirable. In addition, when the powdered physical adsorbent 4 is dispersed to produce a slurry, the average diameter of the physical adsorbent 4 is desirably small, and the average primary particle diameter is desirably about 1 μm or less. Furthermore, it is desirable to disperse in water or a solvent so that aggregation does not occur as much as possible, and a dispersant may be added as necessary.

触媒金属5の担持は、物理吸着剤4の担体3への担持方法と同様に、白金粉末を水に分散させディップにより担持させる方法もあるが、塩化白金酸塩酸溶液やジニトロジアンミン白金硝酸溶液などの白金を含む溶液へハニカム構造体を浸漬後、乾燥、焼成を行うことで、微粒化し高分散で白金を担持できる。   The catalyst metal 5 is supported by a method in which platinum powder is dispersed in water and supported by dipping in the same manner as the method of supporting the physical adsorbent 4 on the carrier 3, but a chloroplatinate acid solution, dinitrodiammine platinum nitrate solution, etc. After immersing the honeycomb structure in a solution containing platinum, drying and firing, the particles can be atomized to carry platinum with high dispersion.

担持の順番としては、ハニカム構造体へ物理吸着剤4を担持後に、上記方法で白金等の触媒金属5を担持する方法が望ましい。これにより、触媒金属5が物理吸着剤4表面にも担持され、比表面積を大きくすることができる。また、ハニカム構造体を硝酸溶液などへ浸漬後、いったん60〜150℃で乾燥後、400℃以上で焼成させることが望ましい。   As the loading order, a method of loading the catalyst metal 5 such as platinum by the above method after loading the physical adsorbent 4 on the honeycomb structure is desirable. Thereby, the catalyst metal 5 is carried also on the surface of the physical adsorbent 4, and the specific surface area can be increased. Moreover, it is desirable to immerse the honeycomb structure in a nitric acid solution or the like, then dry it at 60 to 150 ° C., and then fire it at 400 ° C. or higher.

乾燥工程を設けない場合、水分のみが激しく蒸発し、触媒金属5粒子が表面に出てこないため、触媒作用が小さくなる。さらには、物理吸着剤4を担持するときに酸化チタンやシリカのような親水性の金属酸化物を添加しておき同時に担持する、あるいは物理吸着剤4を担持後に親水性の金属酸化物を担持すると良い。白金などをハニカム構造体へ溶液のディップにより担持後、乾燥させる場合、乾燥時に溶液が蒸発しやすい端面へ集まりその部分への触媒金属5の析出が多くなる傾向があるが、親水性の物質を担持しておくことにより、その部分へも溶液が集まり蒸発していくので、触媒金属5を高分散させ担持することができる。   When the drying process is not provided, only the moisture evaporates violently and the catalytic metal 5 particles do not come out on the surface, so that the catalytic action is reduced. Furthermore, when supporting the physical adsorbent 4, a hydrophilic metal oxide such as titanium oxide or silica is added and supported simultaneously, or after supporting the physical adsorbent 4, a hydrophilic metal oxide is supported. Good. When platinum or the like is supported on the honeycomb structure by dipping the solution and then dried, the solution tends to collect at the end face where the solution easily evaporates during drying, and the catalyst metal 5 tends to be deposited on the portion. By supporting the solution, the solution also collects and evaporates in that portion, so that the catalyst metal 5 can be highly dispersed and supported.

以下、脱臭体に対する実験例を示す。   Hereafter, the experiment example with respect to a deodorizing body is shown.

疎水性ゼオライトを水に分散させ、バインダとして固形分濃度20wt%のコロイダルシリカを加え、水と疎水性ゼオライトとコロイダルシリカとの比が、8:2:1のスラリー(以下、本実施の形態ではスラリーAという)と、水と酸化チタンとコロイダルシリカとの比が、40:2:1のスラリー(以下、本実施の形態ではスラリーBという)と、白金量が0.5wt%のジニトロジアンミン白金硝酸溶液(以下、本実施の形態では溶液Aという)と、水と活性炭と白金粉末とコロイダルシリカとの比が、8:2:0.02:1のスラリー(以下、本実施の形態ではスラリーCという)とを作製した。   Hydrophobic zeolite is dispersed in water, colloidal silica having a solid content concentration of 20 wt% is added as a binder, and a slurry having a ratio of water, hydrophobic zeolite, and colloidal silica of 8: 2: 1 (hereinafter referred to in this embodiment) Slurry A), a slurry having a ratio of water, titanium oxide and colloidal silica of 40: 2: 1 (hereinafter referred to as slurry B in the present embodiment), and dinitrodiammine platinum having a platinum amount of 0.5 wt%. A slurry in which the ratio of nitric acid solution (hereinafter referred to as solution A in this embodiment), water, activated carbon, platinum powder, and colloidal silica is 8: 2: 0.02: 1 (hereinafter referred to as slurry in this embodiment). C)).

次に、アルミナとシリカの繊維からなるハニカム構造体(100×62×t10、205セル/inch)を4つ用意した(以下、本実施の形態ではそれぞれ、ハニカムA、ハニカムB、ハニカムC、ハニカムDという)。 Next, four honeycomb structures (100 × 62 × t10, 205 cells / inch 2 ) made of alumina and silica fibers were prepared (hereinafter, in this embodiment, honeycomb A, honeycomb B, honeycomb C, Honeycomb D).

ハニカムA、ハニカムB、ハニカムCをスラリーAに浸漬、130℃での乾燥を2回繰り返し、それぞれに疎水性ゼオライトを0.1g/cc担持した。その後、ハニカムAを溶液Aに浸漬させ、130℃で乾燥した後、600℃で10分間の焼成を行い、0.06gの白金を担持させた。また、ハニカムBをスラリーBに浸漬させ、130℃で乾燥を行い、酸化チタンを0.01g/cc担持した。その後、ハニカムBを溶液Aに浸漬させ、130℃で乾燥した後、600℃で10分間の焼成を行い、0.06gの白金を担持させた。次に、ハニカムDをスラリーCに浸漬させ、130℃で乾燥を行い、疎水性ゼオライト0.1g/cc、白金0.06gを担持させた。   Honeycomb A, honeycomb B, and honeycomb C were immersed in slurry A and dried at 130 ° C. twice, and each supported 0.1 g / cc of hydrophobic zeolite. Thereafter, the honeycomb A was immersed in the solution A, dried at 130 ° C., and then fired at 600 ° C. for 10 minutes to carry 0.06 g of platinum. Further, the honeycomb B was immersed in the slurry B and dried at 130 ° C. to carry 0.01 g / cc of titanium oxide. Thereafter, the honeycomb B was immersed in the solution A, dried at 130 ° C., and then fired at 600 ° C. for 10 minutes to carry 0.06 g of platinum. Next, the honeycomb D was immersed in the slurry C and dried at 130 ° C. to carry 0.1 g / cc of hydrophobic zeolite and 0.06 g of platinum.

作製した4種類のハニカムサンプルにファンを取り付け、各サンプルをそれぞれ10ppmのアセトアルデヒド濃度に調整した40L容器の中へ入れた。270L/minの流量でサンプルを通過するようにファンを調整し、容器内のアセトアルデヒド濃度減衰からワンパスでの酢酸への転化率を算出した。また、実験開始から60分後の酢酸の濃度も測定した。   A fan was attached to the four types of prepared honeycomb samples, and each sample was placed in a 40 L container adjusted to an acetaldehyde concentration of 10 ppm. The fan was adjusted to pass through the sample at a flow rate of 270 L / min, and the conversion rate from acetic acid concentration attenuation in the container to acetic acid in one pass was calculated. The concentration of acetic acid 60 minutes after the start of the experiment was also measured.

実験後、それぞれのサンプルを容器から取り出し、臭気のない場所でファンを作動させ、約20℃で60分間通気を行った。その後、上記実験を行った。これら一連の実験、通気を10回繰り返した。表1に実験結果を示す。なお、ハニカムAを用いた実験が実施例1、ハニカムBを用いた実験が実施例2、ハニカムCを用いた実験が比較例1、ハニカムDを用いた実験が比較例2である。また、「N.D」は検出限界(0.05ppm)以下を示す。   After the experiment, each sample was taken out of the container, the fan was operated in a place without odor, and aeration was performed at about 20 ° C. for 60 minutes. Thereafter, the above experiment was performed. These series of experiments and aeration were repeated 10 times. Table 1 shows the experimental results. The experiment using the honeycomb A is Example 1, the experiment using the honeycomb B is Example 2, the experiment using the honeycomb C is Comparative Example 1, and the experiment using the honeycomb D is Comparative Example 2. “ND” indicates a detection limit (0.05 ppm) or less.

Figure 2006217995
Figure 2006217995

表1より、白金によりアセトアルデヒドが酢酸へ転化されており、親水性の金属酸化物である酸化チタンを担持したものについては転化率が向上している。これは、白金の分散性が向上したものによる効果と考えられる。また、実施例1、2については10回目の酢酸濃度が0.1ppmと小さく、一方比較例2は5ppmと大きい。これは、ゼオライトは活性炭と比較して、通気により酢酸が脱着され再生率が高いことを示している。   From Table 1, acetaldehyde is converted into acetic acid by platinum, and the conversion rate is improved for those carrying titanium oxide, which is a hydrophilic metal oxide. This is considered to be an effect due to the improved dispersibility of platinum. In Examples 1 and 2, the 10th acetic acid concentration is as small as 0.1 ppm, while Comparative Example 2 is as large as 5 ppm. This indicates that the zeolite has a higher regeneration rate due to the desorption of acetic acid by aeration than the activated carbon.

以上から、アセトアルデヒドを常温で酢酸へと転化し、吸着除去できる脱臭体を実現でき、また通気による脱着で物理吸着作用を有する吸着剤を再生させることができるので、メンテナンスフリーで長期間使用できる脱臭体を提供することができる。   From the above, it is possible to realize a deodorant that can convert acetaldehyde into acetic acid at room temperature and remove it by adsorption, and it is possible to regenerate the adsorbent that has a physical adsorption action by desorption by aeration. The body can be provided.

(実施の形態2)
図2は本発明の第2の実施例における脱臭体の模式図である。部屋10内部に脱臭装置11が設置されている。脱臭装置11は吸気手段13と、吸気口14と、脱臭用のフィルター15と、脱臭された空気を部屋に戻す導入口17と、臭気を含む空気20を部屋から排気する排気口19からなる。また、導入口17と排気口19との間には、これらを切り替える切替弁18がある。
(Embodiment 2)
FIG. 2 is a schematic view of a deodorizing body in the second embodiment of the present invention. A deodorizing device 11 is installed inside the room 10. The deodorizing device 11 includes an intake means 13, an intake port 14, a deodorizing filter 15, an introduction port 17 for returning the deodorized air to the room, and an exhaust port 19 for exhausting air 20 containing odor from the room. Further, a switching valve 18 for switching between these is provided between the introduction port 17 and the exhaust port 19.

吸気手段13はシロッコファン、ターボファン、プロペラファン、クロスフローファン、貫流ファン等が一般の吸気手段として使用され、特に限定するものではない。本実施の形態ではプロペラファンを用いた。また、吸気手段13はフィルター15への送風手段としても用いることができる。   As the intake means 13, a sirocco fan, a turbo fan, a propeller fan, a cross flow fan, a cross-flow fan or the like is used as a general intake means, and is not particularly limited. In this embodiment, a propeller fan is used. The intake means 13 can also be used as a blowing means for the filter 15.

次に動作方法について説明する。部屋10内で臭気が発生した場合、脱臭装置11は臭気を含む空気12を吸気手段13により吸気口14を通して吸い込み、フィルター15を通り脱臭され、脱臭された空気16は導入口17を通り、部屋10へ戻される。フィルター15が飽和吸着に達し、部屋10内に臭気がない場合、切替弁18によって通気方向を室外へ排出する排気口19側へ切り替え、吸気手段13を作動させ通気させることにより、臭気が飽和吸着した物理吸着作用を有する吸着剤から臭気を脱着させ、脱着させた臭気を含む空気20を室外へ排出することができる。   Next, an operation method will be described. When odor is generated in the room 10, the deodorizing device 11 sucks the odorous air 12 through the intake port 14 by the intake means 13, is deodorized through the filter 15, and the deodorized air 16 passes through the inlet 17, Return to 10. When the filter 15 reaches saturation adsorption and there is no odor in the room 10, the switching valve 18 switches the ventilation direction to the exhaust port 19 side that discharges outside, and the suction means 13 is operated to ventilate the odor to be saturated adsorption. The odor can be desorbed from the adsorbent having the physical adsorption action, and the air 20 containing the desorbed odor can be discharged outside the room.

したがって、この動作を繰り返すことにより、メンテナンスフリーで長期間使用できる脱臭装置を実現できる。   Therefore, by repeating this operation, a deodorizing apparatus that can be used for a long time without maintenance can be realized.

以上のように、本発明にかかる脱臭体および脱臭体の製造方法および脱臭体を用いた脱臭装置は、上述したように生活空間で発生する臭気を吸着除去でき、特に有害なアセトアルデヒドを常温で有害性の小さい酢酸へと転化し、吸着除去できる脱臭体を提供することができ、また人の手を煩わすことなく自動的に吸脱着を制御し、メンテナンスフリーで長期間使用できる脱臭装置を提供することができる。   As described above, the deodorizing body, the method for producing the deodorizing body, and the deodorizing apparatus using the deodorizing body according to the present invention can adsorb and remove the odor generated in the living space as described above, and particularly harmful acetaldehyde is harmful at room temperature. It is possible to provide a deodorant that can be converted to less acetic acid and adsorbed and removed, and that it can automatically control adsorption and desorption without bothering human hands and provide a maintenance-free deodorization device that can be used for a long time. be able to.

さらに、脱臭体はエアコン、生ごみ処理機、VOC分解機、介護用脱臭機などへ搭載することにより、メンテナンスフリーで長期間利用できる脱臭機能、有害物質分解機能を付加することができるものである。   Furthermore, the deodorizing body can be added to a maintenance-free deodorizing function and a toxic substance decomposing function by being installed in an air conditioner, a garbage disposal machine, a VOC decomposing machine, a nursing deodorizing machine, etc. .

(a)本発明の第1の実施の形態における脱臭体を示す外観模式図(b)同脱臭体表面の拡大模式図(A) Schematic external view showing a deodorizing body in the first embodiment of the present invention (b) An enlarged schematic view of the surface of the deodorizing body 本発明の第2の実施の形態における脱臭装置を示す断面模式図Sectional schematic diagram which shows the deodorizing apparatus in the 2nd Embodiment of this invention.

符号の説明Explanation of symbols

1 脱臭体
2 通気方向
3 担体
4 物理吸着作用を有する吸着剤
5 触媒作用を有する金属
10 部屋
11 脱臭装置
12 臭気を含む空気
13 吸気手段
14 吸気口
15 フィルター
16 脱臭された空気
17 導入口
18 切替弁
19 排気口
20 臭気を含む空気
DESCRIPTION OF SYMBOLS 1 Deodorizing body 2 Air flow direction 3 Support | carrier 4 Adsorbent which has a physical adsorption action 5 Metal which has a catalytic action 10 Room 11 Deodorizing device 12 Air containing odor 13 Intake means 14 Inlet 15 Filter 16 Deodorized air 17 Inlet 18 Switching Valve 19 Exhaust port 20 Air containing odor

Claims (9)

少なくとも吸着作用を有する吸着剤と触媒作用を有する金属と前記吸着剤を担持する担体とから構成され、前記金属がアルデヒド類をカルボン酸へ転化後、前記吸着剤で吸着除去することを特徴とする脱臭体。 It is composed of at least an adsorbent having an adsorbing action, a metal having a catalytic action, and a carrier supporting the adsorbent, and the metal converts aldehydes to carboxylic acids and is adsorbed and removed by the adsorbent Deodorized body. 吸着剤が疎水性ゼオライトである請求項1記載の脱臭体。 The deodorizing body according to claim 1, wherein the adsorbent is a hydrophobic zeolite. 担体が無機繊維から形成されるハニカム構造体である請求項1または2記載の脱臭体。 The deodorizing body according to claim 1 or 2, wherein the carrier is a honeycomb structure formed of inorganic fibers. 金属が少なくとも吸着剤表面に担持されている構成とした請求項1〜3のいずれか1項に記載の脱臭体。 The deodorizing body according to any one of claims 1 to 3, wherein a metal is supported on at least the adsorbent surface. 吸着剤はゼオライトを含み、前記吸着剤に吸着したカルボン酸が、通気により脱着されることで、前記吸着剤が再生される構成とした請求項1〜4のいずれか1項に記載の脱臭体。 The deodorizer according to any one of claims 1 to 4, wherein the adsorbent includes zeolite, and the adsorbent is regenerated by desorbing the carboxylic acid adsorbed on the adsorbent by aeration. . 担体へ、少なくとも吸着作用を有する吸着剤と親水性の金属酸化物とを担持した後、白金属の酸溶液に浸漬し、焼成により触媒作用を有する金属を前記金属酸化物へ担持する脱臭体の製造方法。 A deodorizing body that supports an adsorbent having at least an adsorbing action and a hydrophilic metal oxide on a carrier, then dipped in an acid solution of white metal, and supports the metal having a catalytic action on the metal oxide by firing. Production method. 金属酸化物を酸化チタンを含む材料とする請求項6記載の脱臭体の製造方法。 The manufacturing method of the deodorizing body of Claim 6 which uses a metal oxide as a material containing a titanium oxide. 少なくとも臭気を含む空気を導入する吸気口と、前記臭気を含む空気を吸気する吸気手段と、前記吸気手段により吸気した空気に含まれる臭気を脱臭するフィルターと、前記フィルターにより脱臭された空気を室内へ導入する導入口と、前記フィルターから脱着した臭気を室外へ排気する排気口とを備え、前記フィルターが請求項1〜5のいずれか1項に記載の脱臭体である脱臭装置。 An air inlet for introducing air containing at least odor, an intake means for taking in air containing the odor, a filter for deodorizing odor contained in air sucked by the intake means, and air deodorized by the filter 6. A deodorizing apparatus comprising: an introduction port that introduces the odor to the filter; and an exhaust port that exhausts the odor desorbed from the filter to the outside, wherein the filter is the deodorizing body according to claim 1. 少なくとも臭気を含む空気を導入する吸気口と、前記臭気を含む空気を吸気する吸気手段と、前記吸気手段により吸気した空気に含まれる臭気を脱臭するフィルターと、前記フィルターにより脱臭された空気を室内へ導入する導入口と、前記フィルターから脱着した臭気を室外へ排気する排気口とを備え、前記フィルターが請求項6または7記載の製造方法で製造した脱臭体である脱臭装置。 An air inlet for introducing air containing at least odor, an intake means for taking in air containing the odor, a filter for deodorizing odor contained in air sucked by the intake means, and air deodorized by the filter 8. A deodorizing apparatus comprising an introduction port for introducing the odor and an exhaust port for exhausting the odor desorbed from the filter to the outside, wherein the filter is a deodorant produced by the production method according to claim 6 or 7.
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JP2009090177A (en) * 2007-10-05 2009-04-30 Nexta Corp Filter
JP2010063963A (en) * 2008-09-09 2010-03-25 Panasonic Corp Dehumidification element and dehumidifying apparatus using the same
JP2014206324A (en) * 2013-04-12 2014-10-30 パナソニック株式会社 Air circulation device
CN107032824A (en) * 2017-05-11 2017-08-11 西安交通大学 A kind of manufacture method of directed tissue ceramic matric composite part
US10207258B2 (en) 2015-06-29 2019-02-19 Corning Incorporated Porous ceramic body to reduce emissions

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0924272A (en) * 1995-07-11 1997-01-28 Kuraray Chem Corp Self-regeneration type adsorbent
JPH09313935A (en) * 1996-05-31 1997-12-09 Matsushita Electric Ind Co Ltd Catalyst for removing lower aldehyde compound and removing method
JPH10309443A (en) * 1997-05-09 1998-11-24 Tokyo Gas Co Ltd Deodirization method for combustion gas and catalyst and catalyst unit therefor
JP2000210534A (en) * 1999-01-25 2000-08-02 Mitsubishi Paper Mills Ltd Photocatalyst deodorizing filter
JP2001157709A (en) * 1999-12-03 2001-06-12 Matsushita Electric Ind Co Ltd Deodorant filter and air ajdustment device using the same
JP2003339831A (en) * 2002-05-31 2003-12-02 Mitsubishi Paper Mills Ltd Air cleaner

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0924272A (en) * 1995-07-11 1997-01-28 Kuraray Chem Corp Self-regeneration type adsorbent
JPH09313935A (en) * 1996-05-31 1997-12-09 Matsushita Electric Ind Co Ltd Catalyst for removing lower aldehyde compound and removing method
JPH10309443A (en) * 1997-05-09 1998-11-24 Tokyo Gas Co Ltd Deodirization method for combustion gas and catalyst and catalyst unit therefor
JP2000210534A (en) * 1999-01-25 2000-08-02 Mitsubishi Paper Mills Ltd Photocatalyst deodorizing filter
JP2001157709A (en) * 1999-12-03 2001-06-12 Matsushita Electric Ind Co Ltd Deodorant filter and air ajdustment device using the same
JP2003339831A (en) * 2002-05-31 2003-12-02 Mitsubishi Paper Mills Ltd Air cleaner

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009090177A (en) * 2007-10-05 2009-04-30 Nexta Corp Filter
JP2010063963A (en) * 2008-09-09 2010-03-25 Panasonic Corp Dehumidification element and dehumidifying apparatus using the same
JP2014206324A (en) * 2013-04-12 2014-10-30 パナソニック株式会社 Air circulation device
US10207258B2 (en) 2015-06-29 2019-02-19 Corning Incorporated Porous ceramic body to reduce emissions
CN107032824A (en) * 2017-05-11 2017-08-11 西安交通大学 A kind of manufacture method of directed tissue ceramic matric composite part
CN107032824B (en) * 2017-05-11 2020-04-28 西安交通大学 Manufacturing method of ceramic matrix composite part with oriented structure

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