JPH08257406A - Deodorizing material and deodorizing method - Google Patents
Deodorizing material and deodorizing methodInfo
- Publication number
- JPH08257406A JPH08257406A JP8010337A JP1033796A JPH08257406A JP H08257406 A JPH08257406 A JP H08257406A JP 8010337 A JP8010337 A JP 8010337A JP 1033796 A JP1033796 A JP 1033796A JP H08257406 A JPH08257406 A JP H08257406A
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- Prior art keywords
- oxide
- deodorizing
- weight
- parts
- malodorous
- 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.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、硫化水素、各種メ
ルカプタン類、アンモニア及びアミン類等の各種悪臭成
分を含むガスから悪臭成分の除去に用いられる脱臭材、
および該脱臭材を用いた脱臭方法に関するものであり、
この脱臭材および脱臭方法は、冷蔵庫、トイレ、動物飼
育舎、汚水処理場その他の脱臭に広く活用することがで
きる。TECHNICAL FIELD The present invention relates to a deodorizing material used for removing malodorous components from a gas containing various malodorous components such as hydrogen sulfide, various mercaptans, ammonia and amines,
And a deodorizing method using the deodorizing material,
This deodorizing material and deodorizing method can be widely used for deodorizing refrigerators, toilets, animal housing, sewage treatment plants and the like.
【０００２】[0002]
【従来の技術】トイレや冷蔵庫等の脱臭には、従来より
活性炭を主体とする吸着材に悪臭成分を吸着させる吸着
法、およびオゾンと触媒を用いて悪臭成分を酸化分解さ
せる方法が主として利用されてきた。ところが、前者は
活性炭の吸着作用を利用するものであって吸着容量に限
界があり、長時間使用する場合や悪臭成分濃度が高い場
合には、活性炭を頻繁に交換する必要がある。また後者
は、オゾンの酸化力を利用するものであり、触媒との適
正な組合せによっては半永久的な脱臭が可能であるが、
オゾン発生器や高圧トランス等の専用設備を必要とし、
設備費や運転経費が嵩むという難点が指摘される。2. Description of the Related Art For the deodorization of toilets and refrigerators, an adsorption method of adsorbing a malodorous component on an adsorbent mainly composed of activated carbon and a method of oxidatively decomposing the malodorous component using ozone and a catalyst have been mainly used. Came. However, the former utilizes the adsorption action of activated carbon and has a limited adsorption capacity, and when used for a long time or when the concentration of malodorous components is high, it is necessary to frequently replace the activated carbon. The latter utilizes the oxidizing power of ozone, and semi-permanent deodorization is possible depending on the proper combination with a catalyst.
Requires dedicated equipment such as an ozone generator and high-voltage transformer,
It is pointed out that the equipment and operating costs are high.
【０００３】ところで最近、オゾンを添加することなく
しかも加熱もせずに常温で悪臭成分を除去することので
きる触媒脱臭法が開発され注目を集めている。しかしな
がらこの方法では、硫化水素やメチルメルカプタン等の
如く反応性の高い悪臭成分の除去には有効であるが、メ
チルメルカプタンから他の悪臭成分である二硫化メチル
を副生したり、あるいは硫化メチル、アンモニア、アミ
ン類等の如く反応性の低い悪臭成分については脱臭効果
が不十分であり、脱臭性能の改善が望まれている。By the way, recently, a catalytic deodorizing method has been developed which is capable of removing a malodorous component at room temperature without adding ozone and without heating, and has been attracting attention. However, in this method, although it is effective in removing highly reactive malodorous components such as hydrogen sulfide and methyl mercaptan, methyl disulfide that is another malodorous component is by-produced from methyl mercaptan, or methyl sulfide, Deodorizing effect is insufficient for malodorous components having low reactivity such as ammonia and amines, and improvement of deodorizing performance is desired.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、この様な従
来技術の問題点に着目してなされたものであって、その
目的は、反応性の高い悪臭成分はもとより、反応性の低
い悪臭成分に対しても、長期に亘たり安定して優れた脱
臭効果を持続し得る様な脱臭材および脱臭方法を提供し
ようとするものである。SUMMARY OF THE INVENTION The present invention has been made by paying attention to the problems of the prior art as described above, and its purpose is to provide a malodorous component having high reactivity as well as a malodorous component having low reactivity. It is an object of the present invention to provide a deodorizing material and a deodorizing method capable of stably maintaining an excellent deodorizing effect for a long period of time even for the components.
【０００５】[0005]
【課題を解決するための手段】上記課題を達成すること
のできた本発明の脱臭材は、酸化銅、酸化マンガンおよ
び硝酸銀と、チタン酸化物、珪素酸化物あるいはそれら
の混合物もしくは複合酸化物とを脱臭成分として含有す
るところにその特徴が存在する。該脱臭材中における酸
化銅、酸化マンガンおよび硝酸銀の好ましい組成比は、
酸化銅：ＣｕＯ換算で酸化銅：ＣｕＯ換算で１〜３０重
量部、酸化マンガン：ＭｎＯ2 換算で３〜５０重量部、
硝酸銀：ＡｇＮＯ3 換算で１〜２０重量部であり、ま
た、該脱臭材中に占める酸化銅、酸化マンガンおよび硝
酸銀の総含有率は５〜６０重量％の範囲が好ましい。The deodorizing material of the present invention which has been able to achieve the above objects comprises copper oxide, manganese oxide and silver nitrate, and titanium oxide, silicon oxide or a mixture or complex oxide thereof. Its characteristic is that it is contained as a deodorizing component. The preferable composition ratio of copper oxide, manganese oxide and silver nitrate in the deodorant is
Copper oxide: 1 to 30 parts by weight in terms of CuO in terms of copper oxide: 3 to 50 parts by weight in terms of manganese oxide: MnO 2 ,
Silver nitrate: 1 to 20 parts by weight in terms of AgNO 3 , and the total content of copper oxide, manganese oxide and silver nitrate in the deodorizing material is preferably in the range of 5 to 60% by weight.
【０００６】そしてこの脱臭材を用いて、硫化水素、各
種メルカプタン類、アンモニア、アミン類などの悪臭成
分含有ガスを処理すれば、これら悪臭成分が分解除去さ
れ、効率よく脱臭を行なうことができる。By treating the malodorous component-containing gas such as hydrogen sulfide, various mercaptans, ammonia and amines with this deodorant, these malodorous components are decomposed and removed, and the deodorization can be efficiently performed.
【０００７】またこの脱臭材は、酸化銅、酸化マンガン
及び硝酸銀またはそれらの前駆体を、チタン酸化物、珪
素酸化物あるいはそれらの混合物もしくは複合酸化物と
共に均一に混練し、所定の形状に成形してから乾燥・焼
成する方法、あるいは、チタン酸化物、珪素酸化物ある
いはそれらの混合物もしくは複合酸化物を原料とし、あ
るいは必要により更にシリカ−アルミナ、シリカ、アル
ミナ、チタニア、ゼオライト等のセラミック系バインダ
ーと共に均一に混練してペレット状、板状、ハニカム状
など任意の形状に成形してから乾燥・焼成しておき、こ
れに酸化銅、酸化マンガン及び硝酸銀またはそれらの前
駆体を含む溶液を塗布または含浸させてから乾燥・焼成
する方法等によって製造することができる。This deodorant material is obtained by uniformly kneading copper oxide, manganese oxide and silver nitrate or their precursors together with titanium oxide, silicon oxide or a mixture or complex oxide thereof, and molding them into a predetermined shape. And then drying and firing, or using titanium oxide, silicon oxide or a mixture or composite oxide thereof as a raw material, or if necessary, further with a ceramic-based binder such as silica-alumina, silica, alumina, titania or zeolite. It is uniformly kneaded to form pellets, plates, honeycombs, etc., and then dried and fired, and a solution containing copper oxide, manganese oxide, and silver nitrate or their precursors is applied or impregnated on them. It can be produced by a method such as drying and firing after the treatment.
【０００８】[0008]
【発明の実施の形態】本発明者らは前述の様な従来技術
の下で、コスト高につくオゾン等を使用することなく又
加熱処理を要することなく、反応性の高い悪臭成分はも
とより反応性の低い悪臭成分に対しても、長期に亘たり
安定して優れた脱臭効果を持続し得る様な脱臭材の開発
を期して種々研究を進めてきた。BEST MODE FOR CARRYING OUT THE INVENTION Under the above-mentioned conventional techniques, the present inventors have reacted with a highly reactive malodorous component without using expensive ozone or the like and without requiring heat treatment. We have been conducting various research in anticipation of the development of deodorizing materials that can stably maintain an excellent deodorizing effect for a long period of time, even for malodorous components with low properties.
【０００９】その結果、酸化銅、酸化マンガン、硝酸銀
の３成分を主たる脱臭活性成分として併用すると共に、
これらを保持するための主たる担体成分としてチタン酸
化物、珪素酸化物あるいはそれらの混合物もしくは複合
酸化物を使用すれば、優れた性能の脱臭材が得られるこ
とを知った。とりわけ、脱臭材中に主たる脱臭活性成分
として含有させる前記３成分の組成比を、酸化銅：Ｃｕ
Ｏ換算で酸化銅：ＣｕＯ換算で１〜３０重量部、酸化マ
ンガン：ＭｎＯ2 換算で３〜５０重量部、硝酸銀：Ａｇ
ＮＯ3 換算で１〜２０重量部の範囲に設定し、また脱臭
材中に占めるこれら３成分の総含有率を５〜６０重量％
の範囲に設定し、更には、主たる担体成分として、チタ
ンと珪素の複合酸化物を使用すれば、優れた脱臭性能を
有する脱臭材が得られることを見出した。As a result, the three components of copper oxide, manganese oxide and silver nitrate were used together as the main deodorizing active ingredients, and
It has been found that a deodorant having excellent performance can be obtained by using titanium oxide, silicon oxide or a mixture or complex oxide thereof as a main carrier component for holding these. In particular, the composition ratio of the three components to be contained as the main deodorizing active component in the deodorizing material is copper oxide: Cu.
Copper oxide in terms of O: 1 to 30 parts by weight in terms of CuO, manganese oxide: 3 to 50 parts by weight in terms of MnO 2 , silver nitrate: Ag
It is set in the range of 1 to 20 parts by weight in terms of NO 3 , and the total content of these three components in the deodorant is 5 to 60% by weight.
It has been found that a deodorant having excellent deodorizing performance can be obtained by setting the above range and using a composite oxide of titanium and silicon as the main carrier component.
【００１０】上記成分のうち酸化銅は多量の表面酸素を
保有しており、硫化水素やメチルメルカプタンを常温で
酸化分解する作用を発揮するが、この酸化分解反応で消
費された酸素は、被処理ガス中に含まれる空気中の酸素
によって逐次補われるので、その脱臭効果を長期間に亘
って持続する。Of the above-mentioned components, copper oxide has a large amount of surface oxygen and exerts an action of oxidatively decomposing hydrogen sulfide and methyl mercaptan at room temperature. The oxygen consumed by this oxidative decomposition reaction is to be treated. Since it is sequentially supplemented by oxygen in the air contained in the gas, its deodorizing effect is maintained for a long period of time.
【００１１】また酸化マンガンは、前記した様な各種悪
臭ガスに対して脱臭効果を有効に発揮するが、とりわ
け、上記酸化銅に起因して生じるメチルメルカプタンか
ら二硫化メチルへの変換を抑制するうえで有効に作用す
る。こうした作用を有効に発揮させるには、酸化銅に対
する配合比率でＭｎＯ2 ／ＣｕＯの重量比を２以上とす
ることが好ましい。Manganese oxide effectively exerts a deodorizing effect on various malodorous gases as described above, but above all, it suppresses the conversion of methyl mercaptan to methyl disulfide caused by the above copper oxide. Works effectively with. In order to effectively exhibit such an effect, it is preferable to set the weight ratio of MnO 2 / CuO to 2 or more in the compounding ratio to copper oxide.
【００１２】次に硝酸銀は、本発明における最も特徴的
な成分であり、その強力な酸化能力によって、従来技術
では除去困難であった反応性の低い悪臭成分、殊にアン
モニア、トリメチルアミン、硫化メチル、アセトアルデ
ヒド等の分解除去が可能となる。Next, silver nitrate is the most characteristic component of the present invention, and its strong oxidizing ability makes it difficult to remove malodorous components which are difficult to remove by the prior art, especially ammonia, trimethylamine, methyl sulfide, It is possible to decompose and remove acetaldehyde and the like.
【００１３】銀や酸化銀を脱臭成分の１つとして利用す
ることは既に公知であるが、これらは脱臭材調製時の熱
処理によって金属銀の巨大粒子になり易い性質を有して
おり、この金属銀は悪臭ガスに対して不活性である。そ
こで銀を複合酸化物として担持させる方法や過酸化物等
によって湿式酸化する方法等を採用し、酸化銀として担
体に担持させる方法が幾つか提案されているが、複雑な
工程が必要であるばかりでなく、微粒子状態での分散担
持が困難であり、満足な脱臭効果は得られていない。し
かるに本発明では、従前の様に銀を酸化銀として活用す
るのではなく、これを硝酸銀の形態で活用することによ
り、銀の脱臭成分としての特性を最大限有効に発揮させ
たところに大きな特徴を有している。It is already known that silver or silver oxide is used as one of the deodorizing components, but these have the property of being easily converted into large particles of metallic silver by heat treatment during the preparation of the deodorizing material. Silver is inert to malodorous gases. Therefore, some methods of supporting silver as a complex oxide, wet oxidation with a peroxide, etc., and supporting it as silver oxide on a carrier have been proposed, but only complicated steps are required. In addition, it is difficult to carry the particles in a dispersed state, and a satisfactory deodorizing effect is not obtained. In the present invention, however, silver is not utilized as silver oxide as in the past, but by utilizing this in the form of silver nitrate, the characteristic as a deodorizing component of silver is exhibited to the maximum extent. have.
【００１４】上記酸化銅、酸化マンガンおよび硝酸銀の
作用を有効に発揮させるには、脱臭材中におけるこれら
３成分の組成比を、酸化銅：ＣｕＯ換算で１〜３０重量
部（より好ましくは１〜２０重量部）、酸化マンガン：
ＭｎＯ2 換算で３〜５０重量部（より好ましくは１０〜
３０重量部）、硝酸銀：ＡｇＮＯ3 換算で１〜２０重量
部（より好ましくは５〜１０重量部）の範囲に設定する
のがよく、酸化銅が１重量部未満、酸化マンガンが３重
量部未満、硝酸銀が１重量部未満では、夫々の効果が不
十分になって悪臭成分に対する酸化分解作用が十分に発
揮されず、満足のいく脱臭効果が得られにくくなる。In order to effectively exhibit the effects of the above-mentioned copper oxide, manganese oxide and silver nitrate, the composition ratio of these three components in the deodorizing material is 1 to 30 parts by weight (more preferably 1 to 30 parts by weight) in terms of copper oxide: CuO. 20 parts by weight), manganese oxide:
3-50 parts by weight in terms of MnO 2 (more preferably 10-
30 parts by weight), and silver nitrate: AgNO 3 in an amount of 1 to 20 parts by weight (more preferably 5 to 10 parts by weight), and copper oxide is less than 1 part by weight, manganese oxide is less than 3 parts by weight. When the amount of silver nitrate is less than 1 part by weight, the respective effects are insufficient and the oxidative decomposition action on the malodorous components is not sufficiently exerted, and it becomes difficult to obtain a satisfactory deodorizing effect.
【００１５】但し、酸化銅の組成比が３０重量部を超え
ると、悪臭成分であるメチルメルカプタンから他の悪臭
成分である二硫化メチルへの変換量が増大し、脱臭効果
が有効に発揮されにくくなり、また酸化マンガンの組成
比が５０重量部を越えてもそれ以上に脱臭効果の向上が
認められない。更に硝酸銀の組成比が２０重量部を超え
て多くなり過ぎると、脱臭材の細孔を閉塞して脱臭効果
がかえって阻害されるといった問題が生じてくる。However, when the composition ratio of copper oxide exceeds 30 parts by weight, the amount of conversion of methyl mercaptan, which is a malodorous component, to methyl disulfide, which is another malodorous component, increases, and it is difficult to effectively exert the deodorizing effect. Further, even if the composition ratio of manganese oxide exceeds 50 parts by weight, the deodorizing effect is not further improved. Further, if the composition ratio of silver nitrate exceeds 20 parts by weight and becomes too large, there arises a problem that the pores of the deodorizing material are closed and the deodorizing effect is rather hindered.
【００１６】また、これら３成分の複合による脱臭作用
を有効に発揮させるには、脱臭材中に占めるこれら３成
分の総含有率を５〜６０重量％、より好ましくは１０〜
３０重量％の範囲とするのがよく、５重量％未満では脱
臭のための活性成分としての絶対量が不足気味となって
脱臭性能が不十分となり、特に悪臭成分濃度の高いガス
に適用したときに満足な脱臭効果が得られにくくなる。
また上記３成分の総含有率が６０重量％を超えて過度に
多くなると、担体成分として作用する前記酸化物の絶対
量が不足気味となり、後述する如く悪臭成分の吸着サイ
トが不足気味となってやはり満足な脱臭性能が得られに
くくなる。In order to effectively exert the deodorizing effect by the combination of these three components, the total content of these three components in the deodorizing material is 5 to 60% by weight, more preferably 10 to
The amount is preferably in the range of 30% by weight, and if it is less than 5% by weight, the absolute amount as an active ingredient for deodorization tends to be insufficient and the deodorizing performance becomes insufficient, especially when applied to a gas having a high malodorous component concentration. It becomes difficult to obtain a satisfactory deodorizing effect.
Further, if the total content of the above three components exceeds 60% by weight and becomes excessively large, the absolute amount of the oxide acting as a carrier component tends to be insufficient, and the adsorption site for the malodorous component tends to be insufficient as described later. After all, it becomes difficult to obtain a satisfactory deodorizing performance.
【００１７】尚、酸化銅の出発原料としては硝酸銅、塩
化銅、硫酸銅、塩基性炭酸銅及び水酸化銅等が、また酸
化マンガンの出発原料としては、硝酸マンガン、硫酸マ
ンガン、炭酸マンガン、水酸化マンガン、活性二酸化マ
ンガン等が夫々好ましいものとして例示される。The starting materials for copper oxide are copper nitrate, copper chloride, copper sulfate, basic copper carbonate and copper hydroxide, and the starting materials for manganese oxide are manganese nitrate, manganese sulfate, manganese carbonate, Manganese hydroxide, activated manganese dioxide and the like are exemplified as preferable examples.
【００１８】本発明で用いられる脱臭活性成分は上記３
成分を必須的に含有するものであるが、被処理ガス中に
含まれる悪臭成分の種類によっては、必要により更に他
の脱臭成分としてニッケル、鉄、コバルト、クロム、亜
鉛、バナジウム等の金属酸化物や白金族金属を適量含有
させることも可能である。また、金属銀、酸化銀あるい
は銅またはマンガンと銀との複合酸化物等が共存してい
ても差し支えない。但しそれらの量は、前記３成分の作
用効果を希釈することがない様、脱臭材中に占める比率
で１０重量％程度以下、より好ましくは５重量％程度以
下に抑えることが望ましい。The deodorizing active ingredient used in the present invention is 3 above.
Although it essentially contains components, depending on the type of malodorous components contained in the gas to be treated, if necessary, other deodorizing components such as nickel, iron, cobalt, chromium, zinc, vanadium, and other metal oxides. It is also possible to contain an appropriate amount of platinum group metal. Further, metallic silver, silver oxide, or a complex oxide of copper or manganese and silver may coexist. However, in order not to dilute the action and effect of the above-mentioned three components, it is desirable to control the amount thereof in the deodorant material to about 10% by weight or less, more preferably about 5% by weight or less.
【００１９】また、これら脱臭のための活性成分を保持
もしくは担持する担体素材としては、チタン酸化物、珪
素酸化物あるいはそれらの混合物もしくは複合酸化物が
好ましく、これらを前記３種の脱臭活性成分と複合する
ことによって、脱臭活性の高い脱臭材を得ることができ
る。これらの酸化物は、前記脱臭活性成分を効率よく保
持もしくは担持して優れた脱臭作用を発揮させる為、そ
の比表面積が５０ｍ2／ｇ（ＢＥＴ法による比表面積測
定）以上、より好ましくは１００〜２００ｍ2／ｇのも
のがよい。しかして比表面積の大きい多孔質のものであ
れば、その表面に無数に存在する細孔が前記３種の脱臭
活性成分の付着サイトになると共に、悪臭成分ガスに対
しても吸着トラップ効果を発揮し、該細孔に吸着トラッ
プされた悪臭成分が直ちにそこに付着・担持された上記
３種の脱臭活性成分の作用を受けて速やかに分解され、
効率よく脱臭が進行するものと考えられる。As the carrier material which holds or carries these active ingredients for deodorization, titanium oxide, silicon oxide or a mixture or complex oxide thereof is preferable, and these are used as the above three types of deodorizing active ingredients. By combining them, a deodorizing material having a high deodorizing activity can be obtained. These oxides have a specific surface area of 50 m 2 / g or more (specific surface area measurement by the BET method) or more, and more preferably 100 to 10 in order to efficiently hold or carry the deodorizing active component and exert an excellent deodorizing effect. It is preferably 200 m 2 / g. However, if it is a porous material with a large specific surface area, innumerable pores on the surface serve as attachment sites for the above three types of deodorizing active components, and also exert an adsorption trap effect for malodorous component gases. Then, the malodorous components adsorbed and trapped in the pores are immediately decomposed by the action of the above three kinds of deodorizing active components attached and carried thereon.
It is considered that deodorization proceeds efficiently.
【００２０】これらの中でも特に好ましいのはチタンと
珪素の複合酸化物であり、とりわけその組成比がチタ
ン：２０〜９５モル％、珪素：５〜８０モル％の範囲の
ものが担体成分として優れた機能を発揮する。該複合酸
化物の製造に用いられるチタン源としては、たとえば塩
化チタン、硫酸チタン、しゅう酸チタン、テトライソプ
ロピルチタネート等が例示され、珪素源としては、たと
えばコロイド状シリカ、水ガラス、四塩化珪素、テトラ
エチルシリケート等が好ましいものとして挙げられる。Of these, a composite oxide of titanium and silicon is particularly preferable, and those having a composition ratio of titanium: 20 to 95 mol% and silicon: 5 to 80 mol% are excellent as carrier components. Exert function. Examples of the titanium source used for producing the composite oxide include titanium chloride, titanium sulfate, titanium oxalate, and tetraisopropyl titanate, and examples of the silicon source include colloidal silica, water glass, and silicon tetrachloride. Tetraethyl silicate etc. are mentioned as a preferable thing.
【００２１】また該複合酸化物の製法としては、たとえ
ば四塩化チタンをシリカゾルと共に混合し、アンモニア
を添加して沈殿を生成せしめ、水洗・乾燥の後３００〜
６５０℃で焼成する方法等を採用することができ、この
ときのチタニア源とシリカ源の配合比率や焼成温度等を
適宜選択すれば、５０ｍ2 ／ｇ以上の好ましい比表面積
を容易に得ることができる。As a method for producing the composite oxide, for example, titanium tetrachloride is mixed with silica sol, and ammonia is added to form a precipitate.
A method of firing at 650 ° C. or the like can be adopted, and a preferable specific surface area of 50 m 2 / g or more can be easily obtained by appropriately selecting the compounding ratio of the titania source and the silica source and the firing temperature at this time. it can.
【００２２】この様にして得られるチタン・珪素複合酸
化物は、高い比表面積を有しており、夫々の単独酸化物
には見られない特性を発揮する。特に酸性度が極めて高
いので、アンモニアやアミン類等の塩基性ガスの吸着性
能に優れており、脱臭活性成分である酸化銅や酸化マン
ガンの共存下でそれら塩基性悪臭成分ガスに対して優れ
た脱臭作用を発揮する。The titanium-silicon composite oxide thus obtained has a high specific surface area and exhibits characteristics not found in each individual oxide. In particular, the acidity is extremely high, so it has excellent adsorption performance for basic gases such as ammonia and amines, and is excellent for those basic malodorous component gases in the presence of copper oxide and manganese oxide which are deodorizing active ingredients. Deodorizes.
【００２３】脱臭材の製造方法としては、酸化銅、酸化
マンガン及び硝酸銀またはそれらの前駆体を、所定量の
前記酸化物と共に混練して成形する方法、あるいは前記
酸化物素材を用いて前述の如くペレット状やハニカム状
等に成形した後、脱臭活性成分あるいはその前駆体を担
持させる方法等を採用することができる。このとき、必
要によりセラミック系バインダーとしてシリカ−アルミ
ナ、アルミナ、ゼオライト等を併用することも可能であ
る。As the method for producing the deodorizing material, copper oxide, manganese oxide and silver nitrate or their precursors are kneaded together with a predetermined amount of the above-mentioned oxide and molded, or the above-mentioned oxide material is used as described above. A method of supporting a deodorizing active ingredient or a precursor thereof after forming it into a pellet shape, a honeycomb shape or the like can be adopted. At this time, silica-alumina, alumina, zeolite or the like may be used in combination as a ceramic-based binder, if necessary.
【００２４】これらの方法の中でも特に好ましいのは後
者の方法、具体的には、前記酸化物素材を常法により任
意の形状に成形した後、脱臭活性成分の前駆体を含む水
溶性塩の混合溶液を塗布もしくは含浸させ、乾燥乃至焼
成する方法である。しかしてこの方法を採用すれば、前
記酸化物主体の多孔質担体の吸着サイト壁面に前述の脱
臭活性成分が担持されることになり、脱臭処理工程では
該吸着サイトに吸着トラップされた悪臭成分に脱臭活性
成分が速やかに作用するからである。Among these methods, the latter method is particularly preferable. Specifically, the above-mentioned oxide material is molded into an arbitrary shape by a conventional method, and then a water-soluble salt containing a precursor of a deodorizing active ingredient is mixed. In this method, a solution is applied or impregnated and dried or baked. However, if this method is adopted, the above-mentioned deodorizing active component will be carried on the adsorption site wall surface of the porous carrier mainly composed of the oxide, and in the deodorizing treatment step, the malodorous component adsorbed and trapped at the adsorption site will be generated. This is because the deodorizing active ingredient acts quickly.
【００２５】[0025]
【実施例】以下、実施例を挙げて本発明をより具体的に
説明するが、本発明はもとより下記実施例によって制限
を受けるものではなく、前・後記の趣旨に適合し得る範
囲で適当に変更を加えて実施することも可能であり、そ
れらはいずれも本発明の技術的範囲に包含される。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples, and may be appropriately applied within a range compatible with the gist of the preceding and the following. Modifications can be made and implemented, and all of them are included in the technical scope of the present invention.
【００２６】実施例１ チタンおよび珪素からなる複合酸化物を下記の方法で調
製した。まず、チタン源としては硫酸チタニル（ＴｉＯ
ＳＯ4 ）をＴｉＯ2 換算で２５０ｇ／リットル含む硫酸
水溶液（全Ｈ2 ＳＯ4 が１１００ｇ／リットル）を用い
た。この硫酸チタニル硫酸水溶液１５３リットルを水３
００リットルで希釈してチタン含有硫酸水溶液とした。
一方、水４００リットルにアンモニア水（ＮＨ3含有率
２５％）を２８０リットル添加し、更に「スノーテック
スＮＣＳ−３０」（日産化学社製のシリカゾル）２４ｋ
ｇを加え、得られた珪素含有溶液を攪拌しながら、前記
で得たチタン含有硫酸水溶液を徐々に滴下して共沈ゲル
を調製した。Example 1 A composite oxide composed of titanium and silicon was prepared by the following method. First, as a titanium source, titanyl sulfate (TiO 2
SO 4 ) was used as an aqueous solution of sulfuric acid containing 250 g / liter of TiO 2 (total H 2 SO 4 is 1100 g / liter). 153 liters of this titanyl sulfate aqueous solution was added to water 3
It was diluted with 00 liters to obtain a titanium-containing sulfuric acid aqueous solution.
On the other hand, 280 liters of ammonia water (NH 3 content 25%) was added to 400 liters of water, and "Snowtex NCS-30" (silica sol manufactured by Nissan Chemical Co., Ltd.) 24k
g was added, and the titanium-containing sulfuric acid aqueous solution obtained above was gradually dropped while stirring the obtained silicon-containing solution to prepare a coprecipitated gel.
【００２７】これを１５時間静置した後、ゲルを濾取し
て水洗し２００℃で乾燥し、５５０℃で６時間焼成して
チタニア−シリカ複合酸化物粉末を得た。この複合酸化
物の組成は、Ｔｉ／Ｓｉモル比が４／１であり、ＢＥＴ
法による比表面積は１８５ｍ 2 ／ｇであった。After allowing this to stand for 15 hours, the gel was collected by filtration.
Washed with water, dried at 200 ° C, baked at 550 ° C for 6 hours
A titania-silica composite oxide powder was obtained. This complex oxidation
The composition of the product is that the Ti / Si molar ratio is 4/1, and the BET
Specific surface area by method is 185m 2 / G.
【００２８】この複合酸化物粉末を用いて、通常の手順
で押出し成形し乾燥・焼成して格子状ハニカム成形体と
した。このハニカム成形体を硝酸銅及び硝酸マンガンを
含む水溶液に浸漬し、１００℃で乾燥してから更に３０
０℃で２時間焼成した。その後、硝酸銀を含む水溶液に
浸して硝酸銀を付着させた後、１００℃で乾燥して脱臭
材を得た。該脱臭材の組成を表１に示す。Using this composite oxide powder, extrusion molding was carried out in the usual procedure, followed by drying and firing to obtain a lattice-shaped honeycomb molded body. The honeycomb formed body is dipped in an aqueous solution containing copper nitrate and manganese nitrate, dried at 100 ° C., and then further dried for 30 minutes.
It was calcined at 0 ° C. for 2 hours. Then, after immersing in an aqueous solution containing silver nitrate to adhere silver nitrate, it was dried at 100 ° C. to obtain a deodorizing material. The composition of the deodorant is shown in Table 1.
【００２９】実施例２〜５ 実施例１に示したのと同様にして、表１に示す如く酸化
銅、酸化マンガン、硝酸銀および酸化物の含有比率の異
なる脱臭材を製造した。Examples 2 to 5 In the same manner as in Example 1, deodorizing materials having different content ratios of copper oxide, manganese oxide, silver nitrate and oxide as shown in Table 1 were produced.
【００３０】比較例１〜３ 実施例１において、脱臭活性成分の一種を省略した以外
は同様にして、表１に示す比較脱臭材を製造した。Comparative Examples 1 to 3 Comparative deodorizing materials shown in Table 1 were produced in the same manner as in Example 1 except that one of the deodorizing active ingredients was omitted.
【００３１】［脱臭材としての評価］脱臭性能は流通系
の反応装置を使用し、各脱臭材を充填した充填層の入口
側及び出口側のガスを採取してガスクロマトグラフ法に
より各悪臭成分ガスの濃度を測定し、悪臭成分の除去効
率を求めた。悪臭ガスとしてはメチルメルカプタン、硫
化メチル、トリメチルアミンの３種類を選定し、入口濃
度を５ｐｐｍとし２５℃、湿度５０％ＲＨで空間速度を
３０，０００Ｈｒ-1の条件で評価した。尚メチルメルカ
プタンについては、充填層出口部で検出される二硫化メ
チルのガス濃度も測定した。実施例、比較例の各脱臭材
について、ガスの流通開始から２４時間経過後に測定し
た結果を表２に示した。[Evaluation as Deodorizing Material] Deodorizing performance is measured by using a flow reactor and collecting gas at the inlet side and outlet side of the packed bed filled with each deodorizing material and by using a gas chromatograph method for each malodorous component gas. Was measured to determine the efficiency of removing malodorous components. Three types of malodorous gas were selected: methyl mercaptan, methyl sulfide, and trimethylamine, and the inlet concentration was 5 ppm, and the space velocity was evaluated at 25 ° C., humidity 50% RH, and space velocity 30,000 Hr −1 . For methyl mercaptan, the gas concentration of methyl disulfide detected at the packed bed outlet was also measured. Table 2 shows the measurement results of each of the deodorizing materials of Examples and Comparative Examples, which was measured 24 hours after the start of gas distribution.
【００３２】[0032]
【表１】 [Table 1]
【００３３】[0033]
【表２】 [Table 2]
【００３４】表１，２からも明らかである様に、本発明
の規定要件を全て満足する脱臭材は、比較例の脱臭材に
比べて各種悪臭ガスに対して高い脱臭性能を有してお
り、担体基材や脱臭活性成分の配合比の最適化によって
卓越した脱臭性能を示すことを確認できる。これらに対
し比較例１〜３の脱臭材は、メチルメルカプタンの脱臭
工程で二硫化メチルの副生が見られ、且つ硫化メチルや
トリメチルアミンに対する脱臭性能も満足し得るもので
ないことが分かる。As is clear from Tables 1 and 2, the deodorizing material satisfying all the requirements of the present invention has a high deodorizing performance against various malodorous gases as compared with the deodorizing materials of Comparative Examples. It can be confirmed that excellent deodorizing performance is exhibited by optimizing the mixing ratio of the carrier base material and the deodorizing active ingredient. On the other hand, in the deodorizing materials of Comparative Examples 1 to 3, by-products of methyl disulfide are seen in the deodorizing step of methyl mercaptan, and it is understood that the deodorizing performance for methyl sulfide and trimethylamine is not satisfactory.
【００３５】[0035]
【発明の効果】本発明は以上の様に構成されており、硫
化水素やメチルメルカプタン等の如く反応性の高い悪臭
成分はもとより、硫化メチル、アンモニア、アミン類等
の如く反応性の低い悪臭成分に対しても優れた脱臭作用
を示し、またメチルメルカプタンから他の悪臭成分であ
る二硫化メチルを副生することもなく、悪臭成分を効率
よく分解除去できるので、冷蔵庫、トイレ、動物飼育
舎、汚水処理場その他の脱臭に広く活用することができ
る。EFFECTS OF THE INVENTION The present invention is constituted as described above, and has not only a highly reactive malodorous component such as hydrogen sulfide and methyl mercaptan but also a less reactive malodorous component such as methyl sulfide, ammonia and amines. It also has an excellent deodorizing effect on, and does not by-produce other malodorous components, methyl disulfide, from methyl mercaptan, and can decompose and remove the malodorous components efficiently, so that a refrigerator, toilet, animal housing, It can be widely used for deodorizing sewage treatment plants and others.
Claims (6)
チタン酸化物、珪素酸化物あるいはそれらの混合物もし
くは複合酸化物とを脱臭成分として含有することを特徴
とする脱臭材。1. Copper oxide, manganese oxide and silver nitrate,
A deodorizing material comprising titanium oxide, silicon oxide, or a mixture or complex oxide thereof as a deodorizing component.
および硝酸銀の組成比が、酸化銅：ＣｕＯ換算で１〜３
０重量部、酸化マンガン：ＭｎＯ2 換算で３〜５０重量
部、硝酸銀：ＡｇＮＯ3 換算で１〜２０重量部である請
求項１に記載の脱臭材。2. The composition ratio of copper oxide, manganese oxide and silver nitrate in the deodorizing material is 1 to 3 in terms of copper oxide: CuO.
The deodorizing material according to claim 1, which is 0 part by weight, 3 to 50 parts by weight in terms of manganese oxide: MnO 2 , and 1 to 20 parts by weight in terms of silver nitrate: AgNO 3 .
および硝酸銀の総含有率が５〜６０重量％である請求項
１または２に記載の脱臭材。3. The deodorizing material according to claim 1, wherein the total content of copper oxide, manganese oxide and silver nitrate in the deodorizing material is 5 to 60% by weight.
らの混合物もしくは複合酸化物のうち、特にチタンと珪
素の複合酸化物を選択したものである請求項１〜３のい
ずれかに記載の脱臭材。4. The deodorizing material according to any one of claims 1 to 3, which is selected from titanium oxide, silicon oxide, or a mixture or complex oxide thereof, particularly a complex oxide of titanium and silicon. .
らの混合物もしくは複合酸化物の比表面積が５０ｍ2 ／
ｇ以上である請求項１〜４のいずれかに記載の脱臭材。5. The specific surface area of titanium oxide, silicon oxide, or a mixture or complex oxide thereof is 50 m 2 /
The deodorizing material according to any one of claims 1 to 4, which is g or more.
を用いて臭気成分含有ガスを処理することを特徴とする
脱臭方法。6. A deodorizing method comprising treating an odor component-containing gas with the deodorizing material according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8010337A JPH08257406A (en) | 1995-01-27 | 1996-01-24 | Deodorizing material and deodorizing method |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1112195 | 1995-01-27 | ||
| JP7-11121 | 1995-01-27 | ||
| JP8010337A JPH08257406A (en) | 1995-01-27 | 1996-01-24 | Deodorizing material and deodorizing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08257406A true JPH08257406A (en) | 1996-10-08 |
Family
ID=26345602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8010337A Withdrawn JPH08257406A (en) | 1995-01-27 | 1996-01-24 | Deodorizing material and deodorizing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08257406A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002191682A (en) * | 2000-12-26 | 2002-07-09 | Matsushita Electric Ind Co Ltd | Air cleaner and air cleaning filter |
| CN102476899A (en) * | 2010-11-30 | 2012-05-30 | 中国石油化工股份有限公司 | Composite treatment method for treating offensive-odor and sulfur-containing pollutants in refinery wastewater and biochemical sludge |
-
1996
- 1996-01-24 JP JP8010337A patent/JPH08257406A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002191682A (en) * | 2000-12-26 | 2002-07-09 | Matsushita Electric Ind Co Ltd | Air cleaner and air cleaning filter |
| CN102476899A (en) * | 2010-11-30 | 2012-05-30 | 中国石油化工股份有限公司 | Composite treatment method for treating offensive-odor and sulfur-containing pollutants in refinery wastewater and biochemical sludge |
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