JP3247610B2 - Hazardous substance remover and harmful substance removal method using the same - Google Patents
Hazardous substance remover and harmful substance removal method using the sameInfo
- Publication number
- JP3247610B2 JP3247610B2 JP13123196A JP13123196A JP3247610B2 JP 3247610 B2 JP3247610 B2 JP 3247610B2 JP 13123196 A JP13123196 A JP 13123196A JP 13123196 A JP13123196 A JP 13123196A JP 3247610 B2 JP3247610 B2 JP 3247610B2
- Authority
- JP
- Japan
- Prior art keywords
- harmful substance
- harmful
- removing agent
- weight
- titanium oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000126 substance Substances 0.000 title claims description 116
- 238000000034 method Methods 0.000 title claims description 31
- 239000000383 hazardous chemical Substances 0.000 title claims 2
- 239000003795 chemical substances by application Substances 0.000 claims description 50
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 49
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 48
- 239000000440 bentonite Substances 0.000 claims description 47
- 229910000278 bentonite Inorganic materials 0.000 claims description 47
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 47
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 22
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229910001868 water Inorganic materials 0.000 claims description 21
- 239000011230 binding agent Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 15
- 239000003463 adsorbent Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 230000007423 decrease Effects 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
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- 230000001172 regenerating effect Effects 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
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- 229940007718 zinc hydroxide Drugs 0.000 claims description 4
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- 239000004908 Emulsion polymer Substances 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
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- 239000013078 crystal Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
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- 239000000047 product Substances 0.000 description 20
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- 239000008187 granular material Substances 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
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- 238000010298 pulverizing process Methods 0.000 description 5
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
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- 150000002896 organic halogen compounds Chemical class 0.000 description 2
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- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- -1 titanyl sulfate Chemical class 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
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- 241000195493 Cryptophyta Species 0.000 description 1
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Landscapes
- Separation Of Gases By Adsorption (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Glanulating (AREA)
- Catalysts (AREA)
- Treating Waste Gases (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、液体中あるいは気
体中の有害物質を除去する有害物質除去剤およびその製
造方法、それを用いた有害物質除去方法ならびに有害物
質除去剤の再生方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a harmful substance removing agent for removing harmful substances in liquid or gas, a method for producing the same, a method for removing harmful substances using the same, and a method for regenerating the harmful substance removing agent.
【０００２】[0002]
【従来の技術】近年、地球環境、生活環境に対する問題
意識が益々高まっており、各種工場や自動車などから排
出される窒素酸化物や有機ハロゲン化合物や生活空間に
おける悪臭成分などの有害物質を除去することが重要な
課題になっている。また、青果物や花卉から放出される
エチレンガスが、これらの鮮度を低下させる作用がある
ため、エチレンガスを除去しないと長期間にわたって保
存できないなどの問題もある。これらの有害物質を除去
するには、活性炭、ゼオライトなどの吸着剤を用いる方
法があるが、この方法では、有害物質を単に吸着するだ
けであるため、有害物質を多量に吸着すると飽和吸着の
状態に達し、これ以上有害物質を吸着しなくなること、
さらに、吸着した有害物質が状態の変化に伴い再び脱離
するという問題がある。このため、酸化チタンなどの光
半導体が有する光触媒作用により有害物質を酸化分解し
て無害化する方法が提案されている。2. Description of the Related Art In recent years, there has been an increasing awareness of problems with the global environment and living environment, and harmful substances such as nitrogen oxides and organic halogen compounds emitted from various factories and automobiles, and malodorous components in living spaces have been removed. Is an important issue. In addition, since ethylene gas released from fruits and vegetables or flowers has an effect of reducing the freshness thereof, there is also a problem that storage cannot be performed for a long period of time unless ethylene gas is removed. To remove these harmful substances, there is a method using an adsorbent such as activated carbon or zeolite.However, this method only adsorbs harmful substances. Harmful substances are no longer adsorbed,
Further, there is a problem that the adsorbed harmful substance is desorbed again with a change in state. For this reason, a method has been proposed in which a harmful substance is oxidized and decomposed by photocatalysis of an optical semiconductor such as titanium oxide to make it harmless.
【０００３】[0003]
【発明が解決しようとする課題】前記の光半導体である
酸化チタンを粉末の状態で用いると、その光触媒活性に
より、有害物質を効率良く無害化できるが、被処理液や
被処理気体からの分離・回収が難しいという問題があ
る。一方、酸化チタンを造粒あるいは成形した状態で用
いると、分離・回収は容易になるものの、被処理液、被
処理気体や造粒体あるいは成形体同士との接触により、
破壊されやすく、また、造粒体あるいは成形体の表面に
存在する酸化チタンだけしか無害化の反応に寄与できな
いことから、光触媒活性が低いなどの問題がある。ま
た、酸化チタンをガラス、セラミックスなどの担体の表
面に担持した状態で用いる方法もある。しかしながら、
この方法では、分離・回収は容易になり、担体表面の酸
化チタンは有効に利用できるものの、被処理液や被処理
気体との接触などにより酸化チタンが担体から剥離して
しまい、光触媒活性が長期間にわたって維持できず、ま
た、担持処理の際の焼成によって酸化チタン自体の光触
媒活性が低下するという問題がある。When the above-described titanium oxide, which is an optical semiconductor, is used in a powder state, harmful substances can be efficiently detoxified by its photocatalytic activity, but separation from a liquid to be treated or a gas to be treated is difficult.・ There is a problem that collection is difficult. On the other hand, if titanium oxide is used in a granulated or molded state, separation and recovery are facilitated, but the liquid to be treated, the gas to be treated and the contact with the granulated or molded bodies,
Since it is easily broken and only titanium oxide present on the surface of the granulated or molded article can contribute to the detoxification reaction, there are problems such as low photocatalytic activity. There is also a method in which titanium oxide is used while being supported on the surface of a carrier such as glass or ceramics. However,
According to this method, separation and recovery are easy, and although titanium oxide on the surface of the carrier can be effectively used, the titanium oxide is separated from the carrier due to contact with the liquid to be treated or the gas to be treated, and the photocatalytic activity is long. There is a problem that the photocatalytic activity of the titanium oxide itself is lowered due to calcination during the supporting process.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、優れた光
触媒活性を有し、その強度が高く長期間にわたって使用
でき、しかも、分離・回収などの取扱い性の良い有害物
質除去剤を探索した結果、少なくとも酸化チタンとベン
トナイトとから成る造粒体あるいはそれらの成形体であ
って、該ベントナイトがモンモリロナイトを７０重量％
以上含有したものが所望の効果を有し、有害物質除去剤
として各種用途に適用できるものであることを見出し、
本発明を完成した。すなわち、本発明は、悪臭成分など
の有害物質の除去能力に優れ、かつ、取扱い性の良い有
害物質除去剤を提供することにある。また、本発明は、
前記の有害物質除去剤を簡便、かつ、廉価に製造する方
法を提供することにある。さらに、本発明は、前記の有
害物質除去剤を用いて、有害物質を除去する方法を提供
することにある。さらに、本発明は、吸着能力が失活し
た有害物質除去剤を再生し、活性化する方法を提供する
ことにある。Means for Solving the Problems The present inventors have searched for a harmful substance removing agent which has excellent photocatalytic activity, has high strength and can be used for a long period of time, and has good handleability such as separation and recovery. As a result, a granulated product composed of at least titanium oxide and bentonite or a molded product thereof, wherein the bentonite contains 70% by weight of montmorillonite
It has been found that those containing above have desired effects and can be applied to various uses as a harmful substance remover,
The present invention has been completed. That is, an object of the present invention is to provide a harmful substance remover that has excellent ability to remove harmful substances such as malodorous components and is easy to handle. Also, the present invention
It is an object of the present invention to provide a simple and inexpensive method for producing the harmful substance removing agent. Still another object of the present invention is to provide a method for removing harmful substances using the above harmful substance remover. Another object of the present invention is to provide a method for regenerating and activating a harmful substance remover whose adsorption ability has been deactivated.
【０００５】本発明は、少なくとも酸化チタンとベント
ナイトとからなる造粒体あるいはそれらの成形体であっ
て、該ベントナイトがモンモリロナイトを７０重量％以
上含有した有害物質除去剤である。前記のベントナイト
を結着剤として用いて酸化チタンを造粒し、あるいは成
形すると、その造粒体あるいは成形体の強度が極めて強
く、しかも、優れた光触媒活性と優れた吸着性能を有す
る造粒体あるいは成形体とすることができる。造粒体あ
るいは成形体の形状は、使用場面に応じて適宜設計する
ことができ、たとえば、球状、円柱状、リング状、板
状、ハニカム状などの形状が挙げられる。また、造粒体
あるいは成形体を粉砕した不定形状でも良い。本発明で
は、有害物質との接触面積を大きくでき、しかも、圧力
損失を低くできることから、ハニカム形状を有する構造
体とするのが好ましい。ハニカム形状を有する構造体と
は、三角形、四角形、六角形、円、楕円などの形の断面
を有する貫通孔を多数存在させた構造体のことである。
造粒体あるいは成形体の大きさは、使用場面に応じて適
宜設計することができる。The present invention is a granulated product comprising at least titanium oxide and bentonite or a molded product thereof, wherein the bentonite contains montmorillonite in an amount of 70% by weight or more. When the titanium oxide is granulated or molded using the bentonite as a binder, the granulated body or the molded body has an extremely high strength, and further, has excellent photocatalytic activity and excellent adsorption performance. Alternatively, it can be a molded article. The shape of the granulated product or the formed product can be appropriately designed according to the use scene, and examples thereof include shapes such as a sphere, a column, a ring, a plate, and a honeycomb. Further, an irregular shape obtained by pulverizing a granulated body or a molded body may be used. In the present invention, a structure having a honeycomb shape is preferable because the contact area with the harmful substance can be increased and the pressure loss can be reduced. The structure having a honeycomb shape is a structure in which a large number of through-holes having a cross section of a triangle, a quadrangle, a hexagon, a circle, an ellipse, or the like exist.
The size of the granulated product or formed product can be appropriately designed according to the use scene.
【０００６】本発明において、酸化チタンは、いわゆる
酸化チタンのほか、含水酸化チタン、水和酸化チタン、
水酸化チタン、メタチタン酸、オルトチタン酸をも包含
する。また、前記の酸化チタンに、鉄、コバルト、ニッ
ケル、銅、亜鉛、ルテニウム、ロジウム、パラジウム、
銀、金、白金などの金属あるいは金属の化合物を含有さ
せても良く、特に、酸化亜鉛および／または水酸化亜鉛
を担持した酸化チタンは、有害物質の吸着能力と光触媒
作用による分解能力を併せ持ったものであり、より好ま
しいものである。[0006] In the present invention, titanium oxide is not only titanium oxide, but also hydrous titanium oxide, hydrated titanium oxide,
Titanium hydroxide, metatitanic acid and orthotitanic acid are also included. Further, the titanium oxide, iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium,
It may contain a metal such as silver, gold, and platinum or a compound of a metal. In particular, titanium oxide supporting zinc oxide and / or zinc hydroxide has both the ability to adsorb harmful substances and the ability to decompose by photocatalysis. And more preferred.
【０００７】本発明に用いる酸化チタンは種々の方法で
得ることができ、たとえば、硫酸チタニル、硫酸チタ
ン、塩化チタン、有機チタン化合物などのチタン化合物
を、熱加水分解する方法、硫酸チタニル、硫酸チタ
ン、塩化チタン、有機チタン化合物などのチタン化合物
にアルカリを添加し中和する方法、塩化チタン、有機
チタン化合物などを気相酸化する方法、前記、の
方法で得られた酸化チタンを８００℃程度以下の温度で
焼成する方法が挙げられる。The titanium oxide used in the present invention can be obtained by various methods, for example, a method of thermally hydrolyzing a titanium compound such as titanyl sulfate, titanium sulfate, titanium chloride, an organic titanium compound, titanyl sulfate, titanium sulfate, etc. , Titanium chloride, a method of adding an alkali to a titanium compound such as an organic titanium compound and neutralizing the same, a method of vapor-phase oxidizing the titanium chloride and the organic titanium compound, and the like. Baking method at the above temperature.
【０００８】一般に酸化チタンはいわゆる光触媒作用を
示し、紫外線を照射すると発現する強い酸化力により有
害物質を酸化分解し、無害化することができるが、中で
もアナタース型結晶形を有する酸化チタンが優れた光触
媒活性を有し、さらに、その粒子径が１〜５０ｎｍの小
さなものがより好ましい。さらに好ましい粒子径は１〜
３０ｎｍである。酸化チタンの粒子径は、粉末Ｘ線回折
で得られるピークの半価幅より下記のシェラーの式を用
いて算出する。 Ｌｃ＝０．９λ／（ｗ・ｃｏｓθ） （Ｌｃは粒子径（ｎｍ）であり、λはＸ線の波長（ｎ
ｍ）であり、ｗはピークの半価幅（ｒａｄ）であり、θ
はピーク位置の角度である。）[0008] In general, titanium oxide exhibits a so-called photocatalytic action, and it can oxidize and decompose harmful substances by the strong oxidizing power that is developed when irradiated with ultraviolet rays, and titanium oxide having an anatase-type crystal form is particularly excellent. It is more preferable that it has photocatalytic activity and has a small particle size of 1 to 50 nm. More preferred particle size is 1 to
30 nm. The particle diameter of titanium oxide is calculated from the half width of the peak obtained by powder X-ray diffraction using the following Scherrer's formula. Lc = 0.9λ / (w · cos θ) (Lc is the particle diameter (nm), and λ is the wavelength (n
m) and w is the half width (rad) of the peak, θ
Is the angle of the peak position. )
【０００９】本発明において、ベントナイトは水を含む
と粘着性を示し、造粒体あるいは成形体の結着剤として
作用するものである。ベントナイトは、モンモリロナイ
トを主成分とする天然鉱物から採取されたものであり、
通常、精製、粉砕された形で入手できる。ベントナイト
の産地や種類に制限はない。ベントナイトは、ふつう主
成分のモンモリロナイトのほかに、石英、α−クリスト
バライト、オパール、長石、雲母、フッ石、方解石、ド
ロマイト、石膏、鉄酸化物、パイライトなどを夾雑して
いるが、本発明においてはモンモリロナイト分の多いベ
ントナイトが好ましい。ベントナイト中のモンモリロナ
イト含有量は、７０〜１００重量％が好ましく、８０〜
１００重量％がより好ましい。モンモリロナイト含有量
が前記の範囲より少ない場合には、結着力が不足して造
粒体あるいは成形体の強度が弱くなるため好ましくな
い。モンモリロナイト含有量は次のようにして算出す
る。まず、ベントナイトを１０〜２０倍の水中に投じ、
撹拌して分散させる。このベントナイト分散液は、石英
その他からなる砂質分、微粒子シリカとモンモリロナイ
トからなる複合粒子および遊離のモンモリロナイト粒分
からなっている。次に、このベントナイト分散液から、
前記の砂質分と複合粒子を自然沈降や遠心分離の方法で
除去して、モンモリロナイトからなる分散液を得、次い
で、この分散液を濃縮し、乾燥してモンモリロナイト粉
を得る。このようにして得たモンモリロナイト粉のベン
トナイトに対する割合をモンモリロナイト含有量とし
た。また、本発明において、有害物質除去剤中のベント
ナイトの含有量は５〜３０重量％が好ましく、さらに１
０〜２０重量％がより好ましい。ベントナイトの含有量
が前記の範囲より少ない場合には、結着力が不足して造
粒体あるいは成形体の強度が弱くなるため好ましくな
く、また、前記の範囲より多い場合には、酸化チタンの
吸着能や光触媒活性が発揮されにくくなったり、造粒体
あるいは成形体の強度が却って弱くなるため好ましくな
い。In the present invention, bentonite exhibits tackiness when it contains water, and acts as a binder for granules or compacts. Bentonite is collected from natural minerals whose main component is montmorillonite,
Usually, it is available in purified and ground form. There are no restrictions on the origin or type of bentonite. Bentonite is usually contaminated with montmorillonite as a main component, quartz, α-cristobarite, opal, feldspar, mica, fluorite, calcite, dolomite, gypsum, iron oxide, pyrite, etc. Bentonite rich in montmorillonite is preferred. The content of montmorillonite in the bentonite is preferably 70 to 100% by weight, and 80 to 100% by weight.
100% by weight is more preferred. If the montmorillonite content is less than the above range, the binding force is insufficient, and the strength of the granulated or molded article is undesirably low. The montmorillonite content is calculated as follows. First, throw bentonite 10-20 times into water,
Stir and disperse. This bentonite dispersion liquid is composed of a sandy component composed of quartz or the like, composite particles composed of fine-particle silica and montmorillonite, and free montmorillonite particles. Next, from this bentonite dispersion,
The sandy matter and the composite particles are removed by natural sedimentation or centrifugation to obtain a dispersion of montmorillonite, which is then concentrated and dried to obtain montmorillonite powder. The ratio of the montmorillonite powder thus obtained to bentonite was defined as the montmorillonite content. In the present invention, the content of bentonite in the harmful substance removing agent is preferably 5 to 30% by weight, and more preferably 1 to 30% by weight.
0-20% by weight is more preferred. If the content of bentonite is less than the above range, it is not preferable because the binding force is insufficient and the strength of the granulated product or the molded product becomes weak, and if it is more than the above range, the adsorption of titanium oxide It is not preferable because the performance and photocatalytic activity are hardly exhibited, and the strength of the granulated or molded article is rather weakened.
【００１０】本発明において、酸化チタンおよびベント
ナイトのほかに、有機質バインダを配合させると、より
一層強固であり、しかも、耐水性に優れた有害物質除去
剤とすることができるため好ましい態様である。有機質
バインダとしては、常用される有機質バインダを用いる
ことができ、たとえば、かんしょ、ばれいしょ、タピオ
カ、小麦、コンスターチなどのでん粉質、ふのり、ガラ
クタン（寒天）、アルギン酸ナトリウムなどの海そう
類、トロロアロイ、トラガントゴム、アラビアゴムなど
の植物粘質物、デキストリン、レバンなどの微生物によ
る粘質物、にかわ、ゼラチン、カゼイン、コラーゲンな
どのたん白質、ビスコース、メチルセルローズ、エチル
セルローズ、ヒドロキシエチルセルローズ、カルボキシ
セルローズなどのセルローズ、可溶性でん粉、カルボキ
シメチルでん粉、ジアルデヒドでん粉などのでん粉、ポ
リビニルアルコール、ポリアクリル酸ナトリウム、ポリ
エチレンオキシド、ユリア系ポリマー、フェノール系ポ
リマーなどの合成品などの水溶性有機質バインダ、ポリ
酢酸ビニル、酢ビ・エチレン系共重合体、酢ビ・アクリ
ル系共重合体、酢ビ・Ｖｅｏｖａ共重合体、その他酢ビ
・重合性ビニルモノマー、アクリル系エマルションポリ
アクリル酸エステル、アクリル・Ｖｅｏｖａ共重合体、
酢ビ・Ｖｅｏｖａ・アクリル系、エチレン・酢ビ・アク
リル系、アクリル・スチレン系、ポリ塩化ビニル、塩ビ
・塩化ビニリデン共重合体、合成ゴムラテックスなどの
エマルションポリマーなどが挙げられる。本発明におい
ては、水分による崩壊性がより一層少ない有害物質除去
剤とすることができることから、エマルションポリマー
を配合するのがより好ましい。有機質バインダの含有量
は、有害物質除去剤に対して、０．５〜２０重量％が好
ましく、さらに、１〜１０重量％がより好ましい。有機
質バインダの含有量が前記の範囲より少ない場合には、
有機質バインダを添加した効果が認められにくいため好
ましくなく、また、前記の範囲より多い場合には、酸化
チタンの吸着能や光触媒活性が発揮されにくくなるため
好ましくない。In the present invention, when an organic binder is blended in addition to titanium oxide and bentonite, a more harmful substance removing agent which is stronger and more excellent in water resistance can be obtained. As the organic binder, commonly used organic binders can be used, for example, starches such as sweet potato, potato, tapioca, wheat, constarch, seaweed, seaweed such as galactan (agar), sodium alginate, trolloalloy, tragacanth gum Plant gums such as gum arabic, dextrin, mucous by microorganisms such as levan, glue, gelatin, casein, collagen and other proteins, viscose, methylcellulose, ethylcellulose, hydroxyethylcellulose, carboxycellulose and other celluloses; Starch such as soluble starch, carboxymethyl starch, dialdehyde starch, polyvinyl alcohol, sodium polyacrylate, polyethylene oxide, urea-based polymer, phenol-based polymer, etc. Water-soluble organic binders such as synthetic products, polyvinyl acetate, vinyl acetate / ethylene copolymers, vinyl acetate / acrylic copolymers, vinyl acetate / Veova copolymers, other vinyl acetate / polymerizable vinyl monomers, acrylic emulsions Polyacrylate, acrylic / Veova copolymer,
Emulsion polymers such as vinyl acetate / Veova / acrylic, ethylene / vinyl acetate / acrylic, acrylic / styrene based, polyvinyl chloride, vinyl chloride / vinylidene chloride copolymer, and synthetic rubber latex. In the present invention, it is more preferable to incorporate an emulsion polymer, since a harmful substance remover with even less disintegration due to moisture can be obtained. The content of the organic binder is preferably from 0.5 to 20% by weight, more preferably from 1 to 10% by weight, based on the harmful substance removing agent. When the content of the organic binder is less than the above range,
It is not preferable because the effect of adding the organic binder is not easily recognized, and when the amount is larger than the above range, the adsorption ability and photocatalytic activity of titanium oxide are hardly exhibited, which is not preferable.
【００１１】本発明においては、前記の有害物質除去
剤、すなわち、少なくとも酸化チタンと特定のベントナ
イトとから成る造粒体あるいはそれらの成形体、また
は、少なくとも酸化チタンと特定のベントナイトと有機
質バインダとから成る造粒体あるいはそれらの成形体に
吸着剤を含有させると、有害物質の吸着能力を高めるこ
とができるため、より好ましい態様となる。吸着剤とし
ては常用される吸着剤を用いることができ、具体的に
は、シリカ、アルミナ、ゼオライト、活性炭が挙げら
れ、それらから選ばれる少なくとも１種を用いるのが好
ましい。本発明の有害物質除去剤中の吸着剤の含有量
は、１〜７０重量％が好ましく、さらに、１〜６０重量
％がより好ましい。この際の酸化チタンの含有量は２０
〜９０重量％とするのが好ましい。吸着剤の含有量が前
記の範囲より少ない場合には、吸着剤を添加した効果が
認められにくいため好ましくなく、また、前記の範囲よ
り多い場合には、酸化チタンの含有量が減少し、その光
触媒活性が低下したり、ベントナイトの含有量が減少
し、その結着力が低下したりするため好ましくない。In the present invention, the above-mentioned harmful substance removing agent, that is, a granulated product comprising at least titanium oxide and a specific bentonite or a molded product thereof, or at least titanium oxide, a specific bentonite and an organic binder is used. When an adsorbent is added to the granules or their compacts, the ability to adsorb harmful substances can be increased, which is a more preferable embodiment. As the adsorbent, a commonly used adsorbent can be used, and specific examples thereof include silica, alumina, zeolite and activated carbon, and it is preferable to use at least one selected from them. The content of the adsorbent in the harmful substance removing agent of the present invention is preferably from 1 to 70% by weight, and more preferably from 1 to 60% by weight. At this time, the content of titanium oxide is 20
The content is preferably set to 90% by weight. When the content of the adsorbent is less than the above range, it is not preferable because the effect of adding the adsorbent is not easily recognized, and when the content is more than the above range, the content of titanium oxide decreases, It is not preferable because the photocatalytic activity decreases, the content of bentonite decreases, and the binding power decreases.
【００１２】また、本発明の有害物質除去剤には、必要
に応じて、種々の補強材、フィラーを含有させても良
い。補強材としては、酸化チタン繊維、チタン酸カリウ
ム繊維、結晶セルロースなどを用いることができる。The harmful substance removing agent of the present invention may contain various reinforcing materials and fillers as necessary. As the reinforcing material, titanium oxide fiber, potassium titanate fiber, crystalline cellulose, or the like can be used.
【００１３】次に、本発明の有害物質除去剤を製造する
には、酸化チタンとベントナイトと水との混合物を造粒
あるいは成形し、次いで、乾燥する方法（１）であっ
て、該ベントナイトがモンモリロナイトを７０重量％以
上含有したものを用いるのが好ましい。前記の造粒、成
形を行うには、たとえば、転動造粒機、押し出し造粒
機、撹拌造粒機、解砕機、圧縮成形機、スプレー造粒
機、金型成形機などの機械を用いて行うことができ、転
動造粒機、押し出し造粒機あるいは圧縮成形機で得られ
た造粒体、成形体は、その強度が比較的強いため好まし
い。得られた造粒体あるいは成形体を５０〜２００℃程
度の温度で乾燥して、有害物質除去剤を得る。このよう
にして得られた有害物質除去剤を、必要に応じて、２０
０〜８００℃の温度で焼成しても良い。この焼成によ
り、造粒体あるいは成形体の強度を高めたり、耐水性を
向上させたりすることができる。しかしながら、焼成温
度が８００℃より高いと、酸化チタンの光触媒活性や吸
着能が低下するため好ましくない。乾燥前の造粒体ある
いは成形体を、必要に応じて、ロッシュ型造粒機、マル
メライザーなどの転動造粒機にかけて、球形の造粒体に
整粒した後、乾燥させても良い。Next, in order to produce the harmful substance-removing agent of the present invention, a method (1) in which a mixture of titanium oxide, bentonite and water is granulated or molded and then dried, wherein the bentonite is It is preferable to use one containing 70% by weight or more of montmorillonite. In order to perform the above-mentioned granulation and molding, for example, using a machine such as a rolling granulator, an extrusion granulator, a stirring granulator, a crusher, a compression molding machine, a spray granulator, and a mold molding machine. Granules and compacts obtained by a rolling granulator, extrusion granulator or compression molding machine are preferable because of their relatively high strength. The obtained granulated body or molded body is dried at a temperature of about 50 to 200 ° C. to obtain a harmful substance removing agent. The harmful substance remover thus obtained may be used, if necessary, in 20
You may bake at the temperature of 0-800 degreeC. By this calcination, the strength of the granulated product or the molded product can be increased, and the water resistance can be improved. However, if the firing temperature is higher than 800 ° C., the photocatalytic activity and adsorption capacity of titanium oxide are undesirably reduced. The granules or the compact before drying may be subjected to a rolling granulator such as a Roche granulator or a marmellaizer, if necessary, to adjust the granules into spherical granules, and then dried.
【００１４】また、本発明の有害物質除去剤を製造する
には、酸化チタンとベントナイトと水との混合物を乾燥
し、次いで粗粉砕して造粒あるいは成形する方法（２）
であって、該ベントナイトがモンモリロナイトを７０重
量％以上含有したものを用いるのが好ましい。混合物の
乾燥は５０〜２００℃程度の温度で行うことができる。
前記の粗粉砕には、常用される粉砕機を用いて行うこと
ができ、得られたものを必要に応じて篩分しても良い。
このようにして得られた有害物質除去剤を、必要に応じ
て、２００〜８００℃の温度で焼成しても良い。この焼
成により、造粒体あるいは成形体の強度を高めたり、耐
水性を向上させることができる。しかしながら、焼成温
度が８００℃より高いと、酸化チタンの光触媒活性や吸
着能が低下するため好ましくない。粗粉砕後の造粒体あ
るいは成形体を、必要に応じて、ロッシュ型造粒機、マ
ルメライザーなどの転動造粒機にかけて、球形の造粒体
に整粒した後、乾燥させても良い。In order to produce the harmful substance removing agent of the present invention, a method of drying a mixture of titanium oxide, bentonite and water and then coarsely pulverizing to granulate or form (2)
Preferably, the bentonite contains montmorillonite at 70% by weight or more. Drying of the mixture can be performed at a temperature of about 50 to 200 ° C.
The coarse pulverization can be performed using a commonly used pulverizer, and the obtained one may be sieved as necessary.
The harmful substance removing agent thus obtained may be fired at a temperature of 200 to 800 ° C, if necessary. By this calcination, the strength of the granulated body or the molded body can be increased, and the water resistance can be improved. However, if the firing temperature is higher than 800 ° C., the photocatalytic activity and adsorption capacity of titanium oxide are undesirably reduced. The granulated or shaped body after the coarse pulverization may be subjected to a rolling granulator such as a Roche granulator or a marmellaizer, if necessary, to form a spherical granulated body, and then dried. .
【００１５】前記の（１）、（２）の方法に用いる酸化
チタンとベントナイトと水との混合物に、有機質バイン
ダおよび／または吸着剤を配合することができる。酸化
チタンとベントナイトと水の他に、有機質バインダおよ
び／または吸着剤を配合した混合物を前記（１）、
（２）の方法で造粒あるいは成形して、有害物質除去剤
を得る。このようにして得られた有害物質除去剤を、必
要に応じて、２００〜８００℃の温度で焼成しても良
い。この焼成により、造粒体あるいは成形体の強度を高
めたり、耐水性を向上させることができる。しかしなが
ら、焼成温度が８００℃より高いと、酸化チタンの光触
媒活性や吸着剤の吸着能が低下するため好ましくない。An organic binder and / or an adsorbent can be blended with the mixture of titanium oxide, bentonite and water used in the above methods (1) and (2). A mixture containing an organic binder and / or an adsorbent, in addition to titanium oxide, bentonite, and water, as described in the above (1),
The harmful substance removing agent is obtained by granulation or molding by the method (2). The harmful substance removing agent thus obtained may be fired at a temperature of 200 to 800 ° C, if necessary. By this calcination, the strength of the granulated body or the molded body can be increased, and the water resistance can be improved. However, if the firing temperature is higher than 800 ° C., the photocatalytic activity of titanium oxide and the adsorbing ability of the adsorbent decrease, which is not preferable.
【００１６】次に、本発明の有害物質除去剤を用いて、
流体中の有害物質を除去するには、有害物質除去剤に、
有害物質を含む流体を接触させて、有害物質を吸着させ
て除去したり、あるいは、該有害物質除去剤に、光を照
射しながら、有害物質を含む流体を接触させて、光触媒
作用により有害物質を分解し、無害化して除去したりす
ることができる。このため、本発明の有害物質除去剤
は、有害物質を含む流体の存在する場所に、たとえば、
各種工場やそれらに隣接した場所に、トイレ、居間、台
所、冷蔵庫、自動車、靴箱などの居住空間に、有害物質
と接触するように置くだけでも良い。流体中の有害物質
としては、アンモニア、アルデヒド類、メルカプタン
類、アミン類、硫化水素、硫化メチルなどの悪臭成分、
窒素酸化物、炭化水素類、有機ハロゲン化合物、ＣＯＤ
負荷物質、微生物、細菌、菌、藻類などを対象とするこ
とができる。特に、本発明の有害物質除去剤は悪臭成分
を効率良く除去することができる。有害物質除去剤に照
射する光は、その波長が４００ｎｍ以下の紫外光が含ま
れていれば良く、光源としては、たとえば、水銀ラン
プ、キセノンランプ、水銀−キセノンランプ、殺菌灯、
ブラックライト、白色蛍光灯などの人工光源、太陽光の
自然光を用いることができる。また、前記の人工光源や
自然光を併用したり、あるいは、それらから放射する光
を集光して用いても良い。有害物質除去剤への光照射
は、必ずしも連続して行う必要はなく、断続的に行って
も良い。有害物質除去剤に有害物質を含む流体を接触さ
せるには、送風機や送液機を用いて行うと強制的に接触
させることができるため、効率良く除去することができ
る。さらに、本発明の有害物質除去剤と光源と送風機と
を組み込んで空気清浄装置とすることもできる。具体的
には、本発明の有害物質除去剤を網状基材から成る任意
の形状の箱の中に充填し、これを空気清浄装置内の気体
の流通経路に設け、該有害物質除去剤に光があたるよう
に光源を配置して、空気清浄装置とすることができる。Next, using the harmful substance removing agent of the present invention,
To remove harmful substances in the fluid, a harmful substance remover
Contacting a fluid containing a harmful substance to adsorb and remove the harmful substance, or contacting a fluid containing a harmful substance with light while irradiating the harmful substance removing agent, and harmful substance by photocatalysis. Can be decomposed, rendered harmless and removed. For this reason, the harmful substance removing agent of the present invention is, for example, in a place where a fluid containing a harmful substance exists,
It may be simply placed in a living space such as a toilet, a living room, a kitchen, a refrigerator, a car, a shoe box, or the like in a factory or a place adjacent thereto so as to come in contact with harmful substances. Toxic substances in the fluid include odorous components such as ammonia, aldehydes, mercaptans, amines, hydrogen sulfide, and methyl sulfide,
Nitrogen oxides, hydrocarbons, organic halogen compounds, COD
Load substances, microorganisms, bacteria, fungi, algae and the like can be targeted. In particular, the harmful substance removing agent of the present invention can efficiently remove malodorous components. The light applied to the harmful substance removing agent may include ultraviolet light having a wavelength of 400 nm or less. Examples of the light source include a mercury lamp, a xenon lamp, a mercury-xenon lamp, and a germicidal lamp.
An artificial light source such as a black light and a white fluorescent lamp and natural light of sunlight can be used. Further, the above artificial light source or natural light may be used in combination, or light radiated from them may be collected and used. Light irradiation to the harmful substance removing agent is not necessarily performed continuously, but may be performed intermittently. When a fluid containing a harmful substance is brought into contact with the harmful substance removing agent, it can be forcibly brought into contact with a blower or a liquid feeder, so that the harmful substance remover can be efficiently removed. Further, an air purifying device can be provided by incorporating the harmful substance removing agent of the present invention, a light source and a blower. Specifically, the harmful substance removing agent of the present invention is filled into a box of an arbitrary shape made of a net-like base material, and this is provided in a gas flow path in an air cleaning device, and the harmful substance removing agent is illuminated with light. By arranging the light sources so that the air purifies, an air purifying device can be obtained.
【００１７】次に、本発明の有害物質除去剤に有害物質
が付着して、有害物質除去能力が低下した場合には、該
有害物質除去剤に光を照射することにより、付着した有
害物質を除去して、有害物質除去能力を回復させ、再生
することもできる。この再生方法に用いる光源は、前記
の光源を利用することができる。この再生方法は、普段
光の当たり難い場所や光源を設置しにくい場所で用いた
有害物質除去剤の吸着能力が失活した際の再生方法とし
て特に有効である。Next, when the harmful substance is attached to the harmful substance removing agent of the present invention and the harmful substance removing ability is reduced, the harmful substance removing agent is irradiated with light to remove the attached harmful substance. It can be removed to restore the ability to remove harmful substances and be regenerated. As the light source used in this reproduction method, the above-described light source can be used. This regenerating method is particularly effective as a regenerating method when the adsorption ability of the harmful substance removing agent used in a place where it is usually difficult to reach light or a place where a light source is difficult to be installed is deactivated.
【００１８】[0018]
【実施例】以下に本発明の実施例を示すが、本発明はこ
れに限定されるものではない。 １．試料の作製 実施例１ 硫酸チタニルを熱加水分解し、生じた沈殿を濾過、洗浄
した後、乾燥、粉砕することにより含水酸化チタン（試
料Ａ）を得た。Ｘ線回折の結果、試料Ａはアナタース型
の酸化チタンであり、Ｘ線粒径は７ｎｍであった。この
試料Ａ８０重量部と市販の高純度ベントナイト（豊順洋
行社製、ＳＵＰＥＲ ＣＬＡＹ、モンモリロナイト分：
約８５％）２０重量部に水６０重量部を加え、混練機
（不二パウダル社製バッチニーダー、ＫＤＨ−２０）に
て５分間混練した。この混合物を湿式前押出造粒機（不
二パウダル社製ペレッターダブル、ＥＸＤＦ−１００）
にて押し出し造粒し、さらに球形整粒機（不二パウダル
社製マルメライザー、Ｑ−４００）にて整粒し、乾燥す
ることにより、平均粒径２〜３ｍｍの球状造粒体（試料
Ｐ）を得た。EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. 1. Preparation of Sample Example 1 Titanium sulfate was thermally hydrolyzed, and the resulting precipitate was filtered, washed, dried, and pulverized to obtain a titanium oxide hydroxide (Sample A). As a result of X-ray diffraction, Sample A was an anatase-type titanium oxide, and the X-ray particle size was 7 nm. 80 parts by weight of this sample A and commercially available high-purity bentonite (manufactured by Toyshun Yoko Co., Ltd., SUPER CLAY, montmorillonite content:
60 parts by weight of water was added to 20 parts by weight of about 85%), and the mixture was kneaded for 5 minutes with a kneading machine (a batch kneader manufactured by Fuji Paudal Co., KDH-20). This mixture is subjected to a wet pre-extrusion granulator (pellet double, EXDF-100 manufactured by Fuji Paudal)
And granulated with a spherical sizing machine (Malmerizer, Q-400 manufactured by Fuji Paudal Co., Ltd.), and dried to obtain a spherical granulated product having an average particle size of 2 to 3 mm (sample P). ) Got.
【００１９】実施例２ 実施例１に記載した試料Ａを純水に分散させ、塩化亜鉛
を溶解した後、水酸化ナトリウム水溶液にて中和し、引
き続き濾過、洗浄、乾燥、粉砕することにより、水酸化
亜鉛に担持された含水酸化チタン（試料Ｂ）を得た。水
酸化亜鉛の担持量はモル比でＺｎ：Ｔｉ＝１５：８５と
した。Ｘ線回折の結果、試料Ｂはアナタース型の酸化チ
タンを含有したものであり、そのＸ線粒径は７ｎｍであ
った。次に、この試料Ｂを実施例１の試料Ａに代えて用
いること以外、実施例１と同様の方法で平均粒径２〜３
ｍｍの球状造粒体（試料Ｑ）を得た。Example 2 The sample A described in Example 1 was dispersed in pure water, and after dissolving zinc chloride, neutralized with an aqueous sodium hydroxide solution, followed by filtration, washing, drying and pulverization. Hydrous titanium oxide supported on zinc hydroxide (sample B) was obtained. The supported amount of zinc hydroxide was Zn: Ti = 15: 85 in molar ratio. As a result of X-ray diffraction, Sample B contained anatase-type titanium oxide and had an X-ray particle size of 7 nm. Next, an average particle diameter of 2 to 3 was obtained in the same manner as in Example 1 except that Sample B was used instead of Sample A of Example 1.
mm spherical granules (sample Q) were obtained.
【００２０】実施例３ 実施例１に記載した試料Ａ３０重量部、実施例１に記載
した高純度ベントナイト２０重量部と市販の粉末活性炭
５０重量部に水５５重量部を加え、次いで、これを実施
例１と同様の方法で造粒して平均粒径２〜３ｍｍの球状
造粒体（試料Ｒ）を得た。Example 3 55 parts by weight of water were added to 30 parts by weight of the sample A described in Example 1, 20 parts by weight of the high-purity bentonite described in Example 1, and 50 parts by weight of a commercially available activated carbon powder. Granulation was performed in the same manner as in Example 1 to obtain a spherical granule (sample R) having an average particle size of 2 to 3 mm.
【００２１】実施例４ 実施例２に記載した試料Ｂ３０重量部、実施例１に記載
した高純度ベントナイト２０重量部と市販の粉末活性炭
５０重量部に水５５重量部を加え、次いで、これを実施
例１と同様の方法で造粒して平均粒径２〜３ｍｍの球状
造粒体（試料Ｓ）を得た。Example 4 55 parts by weight of water were added to 30 parts by weight of the sample B described in Example 2, 20 parts by weight of the high-purity bentonite described in Example 1, and 50 parts by weight of a commercially available powdered activated carbon, and then, Granulation was performed in the same manner as in Example 1 to obtain a spherical granule (sample S) having an average particle size of 2 to 3 mm.
【００２２】実施例５ 実施例１に記載した試料Ａ５０重量部、実施例１に記載
した高純度ベントナイト２０重量部と市販の粉末活性炭
３０重量部に水６５重量部を加え、次いで、これを実施
例１と同様の方法で造粒して平均粒径２〜３ｍｍの球状
造粒体（試料Ｔ）を得た。Example 5 65 parts by weight of water were added to 50 parts by weight of the sample A described in Example 1, 20 parts by weight of the high-purity bentonite described in Example 1, and 30 parts by weight of commercially available powdered activated carbon. Granulation was performed in the same manner as in Example 1 to obtain a spherical granule (sample T) having an average particle size of 2 to 3 mm.
【００２３】実施例６ 実施例１に記載した試料Ａ５０重量部、実施例１に記載
した高純度ベントナイト１５重量部、市販の粉末活性炭
３０重量部および有機質バインダとしてアクリル系エマ
ルションポリアクリル酸エステルを樹脂換算量で５重量
部に水６０重量部を加え、次いで、これを実施例１と同
様の方法で造粒して平均粒径２〜３ｍｍの球状造粒体
（試料Ｕ）を得た。Example 6 50 parts by weight of the sample A described in Example 1, 15 parts by weight of the high-purity bentonite described in Example 1, 30 parts by weight of a commercially available powdered activated carbon, and an acrylic emulsion polyacrylate as an organic binder were used. 60 parts by weight of water was added to 5 parts by weight in terms of reduced amount, and then granulated in the same manner as in Example 1 to obtain a spherical granule (sample U) having an average particle size of 2 to 3 mm.
【００２４】実施例７ 実施例１に記載した試料Ａ５０重量部、実施例１に記載
した高純度ベントナイト１５重量部、市販の粉末活性炭
３０重量部および有機質バインダとしてポリ酢酸ビニル
エマルションを樹脂換算量で５重量部に水６０重量部を
加え、次いで、これを実施例１と同様の方法で造粒して
平均粒径２〜３ｍｍの球状造粒体（試料Ｖ）を得た。Example 7 50 parts by weight of the sample A described in Example 1, 15 parts by weight of the high-purity bentonite described in Example 1, 30 parts by weight of a commercially available powdered activated carbon, and polyvinyl acetate emulsion as an organic binder in terms of resin were used. 60 parts by weight of water was added to 5 parts by weight, and then granulated in the same manner as in Example 1 to obtain a spherical granule (sample V) having an average particle size of 2 to 3 mm.
【００２５】実施例８ 実施例１に記載した試料Ａ５０重量部、実施例１に記載
した高純度ベントナイト２０重量部および市販の粉末活
性炭３０重量部に水５５重量部を加え、混合物を得た。
得られた混合物を圧縮成形機にて成形し、乾燥すること
により、厚み１５ｍｍ、孔径１ｍｍ、２００メッシュの
ハニカム成形体（試料Ｗ）を得た。Example 8 55 parts by weight of water was added to 50 parts by weight of the sample A described in Example 1, 20 parts by weight of the high-purity bentonite described in Example 1, and 30 parts by weight of commercially available activated carbon powder to obtain a mixture.
The obtained mixture was molded with a compression molding machine and dried to obtain a honeycomb molded body (sample W) having a thickness of 15 mm, a hole diameter of 1 mm, and 200 mesh.
【００２６】比較例１ 実施例１において、ベントナイトを加えないこと以外は
実施例１と同様に造粒して、比較試料（Ｙ）を得た。Comparative Example 1 A comparative sample (Y) was obtained by granulating in the same manner as in Example 1 except that no bentonite was added.
【００２７】比較例２ 実施例１において、モンモリロナイト含有量が５０重量
％のベントナイト（豊順鑛業社製、穂高印）を用いるこ
と以外は実施例１と同様に造粒して、比較試料（Ｚ）を
得た。Comparative Example 2 A comparative sample (Z) was prepared by granulating in the same manner as in Example 1 except that bentonite having a montmorillonite content of 50% by weight (manufactured by Toyoko Mining Co., Ltd., Hotaka) was used. ) Got.
【００２８】２．試料の特性評価 吸着作用による有害物質除去能力 実施例で得られた試料をパイレックスガラス製の管に充
填し、光を遮断した状態（暗時）において、管の一方か
ら一定濃度の有害ガスを流し、もう一方（出口）から出
てくるガスの濃度を測定することにより、試料の有害ガ
ス除去能力を評価した。尚、充填層内の有害ガスの線速
度を２０ｃｍ／ｓｅｃ、空間速度を１００００ｈｒ-1と
し、除去能力は以下の数式で表すこととした。 除去能力＝（入口濃度−出口濃度）／入口濃度×１００
（％） 有害ガスとしては、悪臭成分の代表例であるアンモニア
とメチルメルカプタンを用いた。比較試料として、市販
の粒状活性炭（比較試料ＡＣ）と無機系吸着剤ミズカナ
イト（比較試料ＭＺ）とを用い、比較した。得られた結
果を表１に示す。この結果から、本発明の有害物質除去
剤は、吸着作用による有害物質の除去能力に優れている
ことがわかった。2. Characteristic evaluation of sample Removal ability of harmful substances by adsorption action The sample obtained in the example was filled in a Pyrex glass tube, and in a state where light was blocked (in the dark), a certain concentration of harmful gas was flowed from one side of the tube. The harmful gas removal ability of the sample was evaluated by measuring the concentration of the gas coming out of the other (outlet). Here, the linear velocity of the harmful gas in the packed bed was set at 20 cm / sec, the space velocity was set at 10,000 hr -1 , and the removal ability was represented by the following equation. Removal capacity = (inlet concentration-outlet concentration) / inlet concentration × 100
(%) As harmful gases, ammonia and methyl mercaptan, which are typical examples of malodorous components, were used. As a comparative sample, a commercially available granular activated carbon (comparative sample AC) and an inorganic adsorbent mizucanite (comparative sample MZ) were used for comparison. Table 1 shows the obtained results. From this result, it was found that the harmful substance removing agent of the present invention was excellent in the ability to remove harmful substances by the adsorption action.
【００２９】[0029]
【表１】 [Table 1]
【００３０】光触媒作用による有害物質除去能力 実施例で得られた試料をパイレックスガラス製の管に充
填し、管の外側からブラックライトによる光照射を行い
ながら、前記の２．と同様に、管の一方から一定濃度
の有害ガスを流し、もう一方（出口）から出てくるガス
の濃度を測定することにより、試料の有害ガス除去能力
を評価した。得られた結果を表２に示す。この結果か
ら、本発明の有害物質除去剤は、光触媒作用による有害
物質の除去能力に優れていることがわかった。Ability to remove harmful substances by photocatalysis The sample obtained in the example was filled in a tube made of Pyrex glass, and light irradiation with black light was performed from outside the tube. Similarly to the above, the harmful gas removal ability of the sample was evaluated by flowing a certain concentration of harmful gas from one of the tubes and measuring the concentration of the gas coming out of the other (outlet). Table 2 shows the obtained results. From these results, it was found that the harmful substance removing agent of the present invention was excellent in the ability to remove harmful substances by photocatalysis.
【００３１】[0031]
【表２】 [Table 2]
【００３２】次に、実施例８および実施例５で得られた
試料ＷおよびＴをパイレックスガラス製の円筒型容器中
にそれぞれ置き、悪臭成分の代表例である所定濃度のア
セトアルデヒドを導入した。吸着が平衡に達した後、ブ
ラックライトによる光照射を行い、アセトアルデヒドの
分解によって生じた二酸化炭素の濃度を測定して、試料
の有害ガス除去能力を評価した。得られた結果を表３に
示す。この結果から、本発明の有害物質除去剤は、光触
媒作用による有害物質の除去能力に優れており、特にハ
ニカム形状にすることでより一層性能が向上することが
わかった。Next, the samples W and T obtained in Examples 8 and 5 were respectively placed in cylindrical containers made of Pyrex glass, and acetaldehyde having a predetermined concentration, which is a typical example of a malodorous component, was introduced. After the adsorption reached equilibrium, light irradiation with black light was performed, and the concentration of carbon dioxide generated by the decomposition of acetaldehyde was measured to evaluate the ability of the sample to remove harmful gases. Table 3 shows the obtained results. From this result, it was found that the harmful substance removing agent of the present invention was excellent in the ability to remove harmful substances by photocatalysis, and in particular, the performance was further improved by forming a honeycomb shape.
【００３３】[0033]
【表３】 [Table 3]
【００３４】光照射による再生能力 実施例で得られた試料をパイレックスガラス製の管に充
填し、初めに光を遮断した状態（暗時）において、管の
一方から一定濃度の有害ガスを一定時間流し、その時の
除去能力を測定した。次に、管の外側からブラックライ
トにより光照射を一定時間行った後、再度光を遮断し
て、その時の除去能力を測定した。光照射後の除去能力
の値が光照射前に比べ増大していると、光照射による再
生能力があることを示す。得られた結果を表４に示す。
この結果から、本発明の有害物質除去剤は、光照射によ
り有害物質の除去能力が再生することがわかった。Regeneration Ability by Light Irradiation The sample obtained in Example was filled in a tube made of Pyrex glass, and in a state where light was first blocked (in the dark), a certain concentration of harmful gas was passed from one of the tubes for a certain period of time. Then, the removal ability at that time was measured. Next, after light irradiation was performed for a certain period of time from the outside of the tube with black light, the light was blocked again, and the removal ability at that time was measured. When the value of the removal ability after light irradiation is larger than that before light irradiation, it indicates that there is a reproduction ability by light irradiation. Table 4 shows the obtained results.
From these results, it was found that the harmful substance removing agent of the present invention regained its ability to remove harmful substances by light irradiation.
【００３５】[0035]
【表４】 [Table 4]
【００３６】３．試料の強度 実施例の試料Ｐ、Ｑ、Ｒ、Ｓ、Ｔ、Ｕ、Ｖ、Ｗはいずれ
も粉落ちが少なく、また、２ｋｇ重程度の力を加えても
つぶれなかった。一方、比較試料Ｙ、Ｚの強度は弱く、
指で軽くつまむ程度で粉化した。また、実施例の試料
Ｕ、Ｖはいずれも水中に投下しても崩壊せず、耐水性を
有するものであった。3. Sample Strength Samples P, Q, R, S, T, U, V, and W of the examples all had little powder falling and did not collapse when a force of about 2 kg was applied. On the other hand, the strength of the comparative samples Y and Z is weak,
It was powdered by lightly pinching it with your finger. Further, the samples U and V of the examples did not collapse even when dropped into water, and had water resistance.
【００３７】[0037]
【発明の効果】本発明は、少なくとも酸化チタンとベン
トナイトとを含有して成る造粒体あるいはそれらの成形
体であって、該ベントナイトがモンモリロナイトを７０
重量％以上含有したものである有害物質除去剤であっ
て、優れた有害物質除去能力を有し、その有害物質除去
能力を長期間にわたって持続でき、しかも、分離・回収
などの取扱い性の良いものであるため、有害物質除去剤
として幅広い用途に適用できる有用なものである。ま
た、本発明は、酸化チタンとベントナイトと有機質バイ
ンダとを含有し、造粒体あるいは成形体であって、該ベ
ントナイトがモンモリロナイトを７０重量％以上含有し
たものである有害物質除去剤であって、より強固な有害
物質除去剤とすることができる。また、本発明は、酸化
チタンとベントナイトと吸着剤、必要に応じて、有機質
バインダとを含有して成る造粒体あるいはそれらの成形
体であって、該ベントナイトがモンモリロナイトを７０
重量％以上含有したものである有害物質除去剤であっ
て、悪臭成分などの有害物質をより一層効率良く除去で
きるので、工業用途ばかりでなく、一般家庭の用途とし
ても有用なものである。さらに、本発明の製造方法は、
前記の有害物質除去剤を簡便、かつ、廉価に製造できる
など、有用な方法である。さらに、本発明の有害物質除
去方法は、前記の有害物質除去剤を用いた簡便な方法で
あるため、工業用途ばかりでなく、一般家庭の用途にも
適用できる方法である。さらに、本発明の再生方法によ
ると、前記の有害物質除去剤が有害物質の付着により失
活した際に、簡便に再生できるため、該有害物質除去剤
を繰り返し利用できる。According to the present invention, there is provided a granulated product containing at least titanium oxide and bentonite or a molded product thereof, wherein the bentonite is made of montmorillonite.
A harmful substance remover containing more than 10% by weight, has excellent harmful substance removal ability, can maintain the harmful substance removal ability for a long period of time, and has good handleability such as separation and recovery. Therefore, it is a useful substance applicable to a wide range of uses as a harmful substance remover. Further, the present invention is a harmful substance removing agent comprising a titanium oxide, bentonite and an organic binder, a granulated or molded article, wherein the bentonite contains montmorillonite at 70% by weight or more, It can be a stronger harmful substance remover. The present invention also provides a granulated product comprising titanium oxide, bentonite, an adsorbent, and, if necessary, an organic binder or a molded product thereof, wherein the bentonite comprises montmorillonite.
It is a harmful substance remover containing not less than 10% by weight and can remove harmful substances such as malodorous components more efficiently, so that it is useful not only for industrial use but also for general household use. Further, the production method of the present invention,
This is a useful method such that the harmful substance removing agent can be easily and inexpensively manufactured. Furthermore, the method for removing harmful substances of the present invention is a simple method using the above-mentioned harmful substance remover, and therefore can be applied not only to industrial use but also to general household use. Furthermore, according to the regeneration method of the present invention, when the harmful substance removing agent is inactivated by the attachment of the harmful substance, the harmful substance removing agent can be easily regenerated, so that the harmful substance removing agent can be used repeatedly.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｂ０１Ｊ 2/28 Ｂ０１Ｄ 53/36 Ｈ 21/16 53/34 １１６Ａ (56)参考文献 特開 平７−60132（ＪＰ，Ａ) 特開 平４−256755（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 21/00 - 38/74 B01D 53/86 ＪＩＣＳＴファイル（ＪＯＩＳ)────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. 7 Identification code FI B01J 2/28 B01D 53/36 H 21/16 53/34 116A (56) References JP-A-7-60132 (JP, A) JP-A-4-256755 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) B01J 21/00-38/74 B01D 53/86 JICST file (JOIS)
Claims (14)
して含有し、少なくとも酸化チタンとベントナイトと吸
着剤と水を混合した混合物を造粒機あるいは成形機で造
粒・成形してなる造粒体あるいは成形体であって、該ベ
ントナイトがモンモリロナイトを７０重量％以上含有し
たものであることを特徴とする有害物質除去剤。 1-5% by weight of bentonite as a binder
And contains at least titanium oxide and bentonite and intake
A mixture of the adhesive and water is formed using a granulator or molding machine.
A harmful substance remover, which is a granulated or molded article obtained by granulation and molding , wherein the bentonite contains 70% by weight or more of montmorillonite.
する構造体であることを特徴とする請求項１に記載の有
害物質除去剤。2. The harmful substance removing agent according to claim 1, wherein the granulated body or the formed body is a structure having a honeycomb shape.
であることを特徴とする請求項１に記載の有害物質除去
剤。3. The content of bentonite is 10 to 20% by weight.
The harmful substance removing agent according to claim 1, wherein
有機質バインダを含有して成ることを特徴とする請求項
１〜３のいずれか１項に記載の有害物質除去剤。4. In addition to titanium oxide and bentonite,
The harmful substance remover according to any one of claims 1 to 3, further comprising an organic binder.
量％であることを特徴とする請求項４に記載の有害物質
除去剤。5. The harmful substance removing agent according to claim 4, wherein the content of the organic binder is 0.5 to 20% by weight.
あることを特徴とする請求項４に記載の有害物質除去
剤。6. The harmful substance removing agent according to claim 4, wherein the organic binder is an emulsion polymer.
および活性炭より成る群より選ばれる少なくとも１種で
あることを特徴とする請求項１に記載の有害物質除去
剤。7. The harmful substance removing agent according to claim 1, wherein the adsorbent is at least one selected from the group consisting of silica, alumina, zeolite and activated carbon.
吸着剤の含有量が１〜７０重量％であることを特徴とす
る請求項１に記載の有害物質除去剤。8. A titanium oxide content of 20 to 90% by weight,
The harmful substance remover according to claim 1, wherein the content of the adsorbent is 1 to 70% by weight.
その粒子径が１〜５０ｎｍであることを特徴とする請求
項１〜８のいずれか１項に記載の有害物質除去剤。9. The titanium oxide has an anatase crystal form,
The harmful substance removing agent according to any one of claims 1 to 8, wherein the particle diameter is 1 to 50 nm.
水酸化亜鉛を担持した酸化チタンであることを特徴とす
る請求項１〜９のいずれか１項に記載の有害物質除去
剤。10. The agent for removing harmful substances according to claim 1, wherein the titanium oxide is zinc oxide and / or titanium oxide carrying zinc hydroxide.
有害物質除去剤に、有害物質を含む流体を接触させて、
該有害物質を除去することを特徴とする有害物質除去方
法。11. A harmful substance-removing agent according to any one of claims 1 to 10, which is contacted with a fluid containing harmful substances,
A method for removing harmful substances, comprising removing the harmful substances.
有害物質除去剤に、光を照射しながら、有害物質を含む
流体を接触させて、該有害物質を除去することを特徴と
する有害物質除去方法。12. A method for removing a harmful substance by contacting a harmful substance-containing fluid with the harmful substance removing agent according to any one of claims 1 to 10 while irradiating the light with the fluid. Hazardous substance removal method.
する請求項１１または１２に記載の有害物質除去方法。13. The method for removing harmful substances according to claim 11, wherein the harmful substances are malodorous components.
有害物質除去剤が、有害物質の付着により有害物質除去
能力が低下した場合において、該有害物質除去剤に光を
照射して、付着した有害物質を除去することを特徴とす
る有害物質除去剤の再生方法。14. The harmful substance removing agent according to any one of claims 1 to 10, wherein the harmful substance removing ability is reduced by irradiating the harmful substance removing agent with light when the harmful substance removing ability decreases due to the adhesion of the harmful substance. And a method for regenerating a harmful substance removing agent, which comprises removing adhering harmful substances.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13123196A JP3247610B2 (en) | 1995-04-28 | 1996-04-26 | Hazardous substance remover and harmful substance removal method using the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12938395 | 1995-04-28 | ||
| JP7-129383 | 1995-04-28 | ||
| JP13123196A JP3247610B2 (en) | 1995-04-28 | 1996-04-26 | Hazardous substance remover and harmful substance removal method using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0910582A JPH0910582A (en) | 1997-01-14 |
| JP3247610B2 true JP3247610B2 (en) | 2002-01-21 |
Family
ID=26464799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13123196A Expired - Fee Related JP3247610B2 (en) | 1995-04-28 | 1996-04-26 | Hazardous substance remover and harmful substance removal method using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3247610B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101570130B1 (en) | 2015-05-12 | 2015-11-18 | 동원중공업 주식회사 | Multiple odor absorbents by using mixing the natural zeolite and method of fabricating the same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003095074A1 (en) * | 2002-05-08 | 2003-11-20 | Donald Lawrence Lush | Air purifying composition |
| CN107555500A (en) * | 2017-09-19 | 2018-01-09 | 江苏科力特环保科技有限公司 | A kind of novel absorbent charcoal stain remover |
-
1996
- 1996-04-26 JP JP13123196A patent/JP3247610B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101570130B1 (en) | 2015-05-12 | 2015-11-18 | 동원중공업 주식회사 | Multiple odor absorbents by using mixing the natural zeolite and method of fabricating the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0910582A (en) | 1997-01-14 |
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