JPH10328568A - Method for regenerating catalyst - Google Patents
Method for regenerating catalystInfo
- Publication number
- JPH10328568A JPH10328568A JP9143832A JP14383297A JPH10328568A JP H10328568 A JPH10328568 A JP H10328568A JP 9143832 A JP9143832 A JP 9143832A JP 14383297 A JP14383297 A JP 14383297A JP H10328568 A JPH10328568 A JP H10328568A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- air
- honeycomb
- regenerating
- heating
- 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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Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、オゾンによる脱臭
処理に用いた活性の低下した、即ち、使用済みのマンガ
ンを主成分とするハニカム触媒の再生方法に関する。[0001] The present invention relates to a method for regenerating a honeycomb catalyst having a reduced activity, that is, used manganese as a main component, which is used in a deodorizing treatment with ozone.
【０００２】[0002]
【従来の技術】大気を含め、悪臭成分を含むガスの脱臭
方法として、オゾンを用いて触媒の存在下にそのような
悪臭ガスを処理して脱臭する方法が広く実用化されてお
り、上記触媒として、種々あるなかでも、性能及び耐久
性の点から、従来、マンガン、特に、二酸化マンガンを
主成分とする触媒が多く用いられている。この触媒は、
通常、オゾン脱臭触媒といわれている。2. Description of the Related Art As a method for deodorizing gas containing malodorous components including air, a method of treating such malodorous gas in the presence of a catalyst using ozone to deodorize the gas has been widely put into practical use. Among them, from the viewpoints of performance and durability, catalysts containing manganese, particularly manganese dioxide as a main component, have been widely used. This catalyst
Usually, it is called an ozone deodorizing catalyst.
【０００３】このようなオゾン脱臭触媒が長期間の使用
によって触媒活性が低下したとき、触媒費用と脱臭処理
の運転費用を低減し、悪臭ガス処理の経済性を高めるた
めに、上記触媒活性の低下によって所謂使用済みとなっ
た触媒を再生し、再利用することが有利である。[0003] When the catalytic activity of such an ozone deodorizing catalyst is reduced due to long-term use, the catalyst activity is reduced in order to reduce the cost of the catalyst and the operating cost of the deodorizing treatment and to enhance the economical efficiency of the treatment of the malodorous gas. It is advantageous to regenerate and reuse the so-called used catalyst.
【０００４】触媒の存在下にオゾンを用いて悪臭ガスを
脱臭する処理は、従来、種々の環境下において用いられ
ているが、特に、居住環境においては、通常、オゾンを
酸素に分解すると共に、このオゾンの強力な酸化作用に
よって、脂肪族アルコールを主成分とする悪臭成分を炭
酸ガスと水とに完全酸化分解して除去することを目的と
する処理が行なわれている。[0004] A treatment for deodorizing odorous gas using ozone in the presence of a catalyst has been conventionally used in various environments. In particular, in a residential environment, usually, ozone is decomposed into oxygen, and Due to the strong oxidizing action of ozone, a process is carried out for the purpose of completely oxidatively decomposing and removing malodorous components mainly composed of aliphatic alcohol into carbon dioxide gas and water.
【０００５】しかし、このような処理においても、実際
には、上記悪臭成分の主成分である脂肪族アルコール類
は、完全には水と炭酸ガスまで酸化分解されず、殆どが
それらの中間酸化物にとどまっており、その結果、低級
脂肪酸のほか、アルデヒド類やケトン類が生成して、触
媒上に付着し、蓄積される。また、悪臭成分である脂肪
族アルコール類も、一部は、そのまま、触媒上に蓄積さ
れる。このようにして、低級脂肪酸のほか、種々の有機
物が触媒上に付着し、蓄積される結果として、触媒の活
性が低下することとなる。更に、触媒上に付着し、蓄積
された低級脂肪酸は、触媒それ自体に悪臭をもたせるこ
ととなる。また、この低級脂肪酸は、一部は、触媒成分
である二酸化マンガンとの化学反応によってマンガン塩
を生成する場合もあり、このような場合には、触媒のオ
ゾン分解活性は一層低下することとなる。However, even in such a treatment, the aliphatic alcohols, which are the main components of the malodorous component, are not completely oxidized and decomposed to water and carbon dioxide gas, but most of them are intermediate oxides thereof. As a result, in addition to lower fatty acids, aldehydes and ketones are produced, adhere to and accumulate on the catalyst. In addition, some of the aliphatic alcohols, which are offensive odor components, are directly accumulated on the catalyst. In this way, in addition to the lower fatty acids, various organic substances adhere to and accumulate on the catalyst, and as a result, the activity of the catalyst decreases. Furthermore, the lower fatty acids deposited and accumulated on the catalyst cause the catalyst itself to have a bad smell. In addition, the lower fatty acid may partially generate a manganese salt by a chemical reaction with manganese dioxide as a catalyst component, and in such a case, the ozonolysis activity of the catalyst is further reduced. .
【０００６】居住環境においてオゾンによる脱臭処理に
用いた使用済みの二酸化マンガンを主成分とするハニカ
ム触媒（活性低下の比較的著しいもの）の触媒への付着
蓄積物質の分析結果の一例を表１に示す。[0006] Table 1 shows an example of the analysis results of substances accumulated and deposited on the catalyst of a used manganese dioxide-based honeycomb catalyst (having a relatively large decrease in activity) used for deodorization treatment with ozone in a living environment. Show.
【０００７】[0007]
【表１】 [Table 1]
【０００８】表１に示す結果から明らかなように、使用
済みの触媒への付着、蓄積物質のうち、最も量の多いも
のは酢酸ほか、炭素数２〜５の低級脂肪酸であり、この
ほかには、アセトンとメタノールが比較的多い。使用済
みの触媒の悪臭の原因は、主として、触媒上に蓄積され
た上記酢酸による。本発明の方法は、このように、使用
済みの触媒への付着、蓄積物質のうち、５０重量％以
上、好ましくは、７５重量％以上が炭素数２〜５の低級
脂肪酸であるような触媒の再生に好適である。As is clear from the results shown in Table 1, among the substances adhering to and accumulating on the used catalyst, those having the largest amounts are acetic acid and lower fatty acids having 2 to 5 carbon atoms. Is relatively high in acetone and methanol. The cause of the malodor of the used catalyst is mainly due to the acetic acid accumulated on the catalyst. Thus, the method of the present invention provides a method for preparing a catalyst in which 50% by weight or more, preferably 75% by weight or more, of a substance adhering to and accumulating on a used catalyst is a lower fatty acid having 2 to 5 carbon atoms. Suitable for reproduction.
【０００９】従来、マンガンを主成分とするオゾン脱臭
に用いた使用済みの触媒の再生方法として、例えば、特
開昭５８−２１９９４２号公報に記載されているよう
に、使用済みの触媒をアンモニア水で洗浄した後、水
洗、乾燥し、この後、不活性雰囲気中で２００〜３００
℃の温度で焼成する方法が知られている。しかし、この
方法によるときは、前述したように、触媒上で生成した
脂肪酸マンガン塩、特に、酢酸マンガンが水中に溶出し
て、触媒成分の損失を招くのみならず、アンモニアを用
いるので、環境汚染のおそれがあり、従って、この方法
は、工業的には採用し難い。Conventionally, as a method for regenerating a used catalyst used for deodorization of ozone containing manganese as a main component, for example, as described in JP-A-58-219942, a used catalyst is treated with aqueous ammonia. , And then washed with water and dried, and then 200 to 300 in an inert atmosphere.
A method of firing at a temperature of ° C. is known. However, when using this method, as described above, the fatty acid manganese salt generated on the catalyst, particularly manganese acetate, elutes in water, causing not only the loss of the catalyst component but also the use of ammonia. Therefore, this method is difficult to employ industrially.
【００１０】また、特開平２−４４５０号公報には、使
用済みの触媒を焼成炉を用いて、空気中、１００〜５０
０℃で焼成する方法が提案されているが、この方法によ
れば、触媒上に蓄積されている前述したような種々の有
機物が燃焼し、焼成条件下で触媒成分である二酸化マン
ガンが焼結し、触媒性能が失なわれて、永久劣化して、
触媒の再生に至らない不都合が再々にして起こる。ま
た、触媒がパルプや芳香族ポリアミド繊維等の有機質の
補強材を含む場合、これらも燃焼し、触媒の強度を失な
わせることとなる。[0010] Japanese Patent Application Laid-Open No. 2-4450 discloses that a used catalyst is treated with a calcining furnace in air at 100 to 50%.
A method of firing at 0 ° C. has been proposed. According to this method, various organic substances accumulated on the catalyst as described above are burned, and manganese dioxide as a catalyst component is sintered under firing conditions. And the catalyst performance is lost, it is permanently deteriorated,
The disadvantage of not regenerating the catalyst occurs again. Further, when the catalyst contains organic reinforcing materials such as pulp and aromatic polyamide fiber, these also burn, and the strength of the catalyst is lost.
【００１１】[0011]
【発明が解決しようとする課題】本発明は、オゾンによ
る脱臭処理に用いた使用済みのマンガンを主成分とする
ハニカム触媒を、その触媒上に付着、蓄積されている有
機物の燃焼を招くことなく、実質的に最初の高いオゾン
分解活性を有せしめて、それ自体、悪臭のない触媒に再
生する方法を提供することを目的とする。DISCLOSURE OF THE INVENTION The present invention provides a method of removing a used manganese-based honeycomb catalyst used for deodorization treatment with ozone, without causing the combustion of organic substances deposited and accumulated on the catalyst. It is an object of the present invention to provide a method for regenerating a catalyst having substantially the first high ozonolysis activity and itself having no bad smell.
【００１２】[0012]
【課題を解決するための手段】本発明によれば、オゾン
による脱臭処理に用いて、その上に有機物が付着し、蓄
積して、活性の低下したマンガンを主成分とするハニカ
ム触媒の再生方法において、空気入口と出口とを備えた
再生炉に、上記ハニカム触媒の貫通孔が上記再生炉にお
ける上記空気流に対して垂直となると共に、ハニカム触
媒がその間に相互に空隙を有するようにその複数を装填
し、上記再生炉に空気を上記ハニカム触媒の間の空隙に
おける線速度が３〜２０ｍ／秒の範囲となるように供給
しながら、空気を１５〜５０℃／時の加熱速度で１５０
〜３５０℃の最終再生温度まで加熱し、この温度で上記
ハニカム触媒が活性を回復するに足る時間、上記加熱空
気で加熱し、このように、加熱した空気で触媒を加熱し
ながら、触媒から上記有機物を蒸発、揮散させることを
特徴とする触媒の再生方法が提供される。According to the present invention, there is provided a method for regenerating a honeycomb catalyst containing manganese as a main component, which is used for a deodorizing treatment with ozone, on which an organic substance adheres and accumulates and whose activity is reduced. In the regeneration furnace having an air inlet and an outlet, a plurality of honeycomb catalysts are provided such that the through holes of the honeycomb catalyst are perpendicular to the air flow in the regeneration furnace, and the honeycomb catalysts have a gap therebetween. While supplying air to the regeneration furnace so that the linear velocity in the gap between the honeycomb catalysts is in the range of 3 to 20 m / sec, while supplying air at a heating rate of 15 to 50 ° C./hour.
To a final regeneration temperature of ~ 350 ° C, at which temperature the honeycomb catalyst is heated with the heated air for a time sufficient to restore activity, thus heating the catalyst with the heated air while removing the catalyst from the catalyst. A method for regenerating a catalyst, characterized by evaporating and volatilizing organic substances, is provided.
【００１３】[0013]
【発明の実施の形態】以下に、本発明の方法を実施する
ための装置構成の一例を示す図１を参照しながら、本発
明について説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to FIG. 1 showing an example of an apparatus configuration for carrying out the method of the present invention.
【００１４】空気は、本発明によれば、再生炉１は、そ
の対向する位置に空気入口２と出口３を備え、加熱装置
（バーナー）４で所定の温度に加熱され、送風装置５に
よって再生炉に供給され、再生炉内に空隙６を置いて順
序よく装填されたハニカム触媒７を加熱した後、管系８
を循環し、再度、加熱装置で加熱される。According to the present invention, the air is regenerated by the regeneration furnace 1 having an air inlet 2 and an outlet 3 at opposite positions, heated to a predetermined temperature by a heating device (burner) 4, and regenerated by a blower 5. After heating the honeycomb catalysts 7 supplied to the furnace and loaded in order with the gap 6 in the regeneration furnace, the pipe system 8 is heated.
And heated again by the heating device.
【００１５】一般に、オゾン脱臭処理に用いるハニカム
触媒は、処理すべき悪臭ガスを通過させるための多数の
平行な貫通孔を備えた構造を有するが、本発明によれ
ば、このようなハニカム触媒は、その貫通孔が再生炉に
おける空気流に対して垂直となると共に、ハニカム触媒
がその間に相互に空隙を有するように順序よく、その複
数が再生炉内に装填される。本発明において、再生炉に
おける空気流とは、上記再生炉の空気入口から出口に向
かう空気の流れ９をいい、空気の線速とは、そのような
ハニカム触媒間の空隙を流れる空気の線速をいう。Generally, the honeycomb catalyst used for the ozone deodorization treatment has a structure having a number of parallel through holes for passing the malodorous gas to be treated. According to the present invention, such a honeycomb catalyst is A plurality of the honeycomb catalysts are loaded in the regeneration furnace in order such that the through-holes are perpendicular to the air flow in the regeneration furnace and the honeycomb catalysts have a gap therebetween. In the present invention, the air flow in the regenerating furnace refers to an air flow 9 from the air inlet to the outlet of the regenerating furnace, and the linear velocity of the air refers to the linear velocity of the air flowing through the gap between the honeycomb catalysts. Say.
【００１６】本発明によれば、このようにハニカム触媒
の複数を再生炉内に順序よく装填した後、再生炉におけ
る空気の加熱速度と線速とを適切に制御しながら、再生
炉に所要の温度に加熱した空気を流通させて、使用済み
の触媒を加熱し、かくして、触媒上に付着し、蓄積され
ている種々の有機物をいわば温度別に分別揮散させて、
触媒を再生する。触媒から蒸発、揮散した有機物は、空
気と共に再生炉から排出され、その一部は、必要に応じ
て、外部に排出されるが、残部は、空気を加熱装置で加
熱する際に、燃焼して、分解される。According to the present invention, after a plurality of honeycomb catalysts are loaded in order into the regenerating furnace in this manner, the required temperature of the regenerating furnace is controlled while appropriately controlling the heating speed and the linear speed of the air in the regenerating furnace. The heated air is passed through to heat the used catalyst, and thus, various organic substances adhering to and accumulating on the catalyst are separated and volatilized according to the so-called temperature,
Regenerate the catalyst. The organic matter evaporated and volatilized from the catalyst is discharged from the regenerating furnace together with the air, and a part of the organic matter is discharged to the outside as necessary, but the remainder is burned when the air is heated by the heating device. Is decomposed.
【００１７】即ち、本発明によれば、再生炉に空気を上
記ハニカム触媒の間の空隙における線速度が３ｍ／秒以
上、好ましくは、３〜２０ｍ／秒の範囲となるように供
給しながら、ハニカム触媒を５０℃／時以下、好ましく
は、１５〜５０℃／時の加熱速度で１５０〜３５０℃、
好ましくは、１８０〜２５０℃の最終再生温度まで加熱
し、この温度で上記ハニカム触媒が活性を回復するに足
る時間、加熱し、このように、加熱した空気で触媒を加
熱しながら、触媒上に付着し、蓄積されている有機物を
蒸発し、分別揮散させることによって、触媒を再生する
のである。That is, according to the present invention, while supplying air to the regeneration furnace such that the linear velocity in the gap between the honeycomb catalysts is 3 m / sec or more, preferably in the range of 3 to 20 m / sec, A honeycomb catalyst at a heating rate of 50 ° C./hour or less, preferably 15 to 50 ° C./hour;
Preferably, the catalyst is heated to a final regeneration temperature of 180-250 ° C., at which temperature the honeycomb catalyst is heated for a time sufficient to regain its activity, thus heating the catalyst with heated air while heating the catalyst on the catalyst. The catalyst is regenerated by evaporating the adhered and accumulated organic matter and separating and evaporating it.
【００１８】本発明において、再生炉における空気の線
速として、通常、再生炉における任意の２つのハニカム
触媒の間の線速を採用してよい。また、再生炉における
空気の温度も、再生炉における任意の単一又は複数の箇
所で温度計１０で測定し、これを制御装置（プログラム
・コントローラ）１１で監視しながら、空気が再生炉内
で所要の加熱速度と温度とを有するように、加熱装置に
よる空気の加熱量を調節する。In the present invention, the linear velocity between any two honeycomb catalysts in the regeneration furnace may be usually used as the linear velocity of the air in the regeneration furnace. Also, the temperature of the air in the regeneration furnace is measured by a thermometer 10 at any one or a plurality of points in the regeneration furnace, and while the temperature is monitored by a control device (program controller) 11, the air is cooled in the regeneration furnace. The amount of heating of the air by the heating device is adjusted so as to have the required heating rate and temperature.
【００１９】ハニカム触媒を空気にて加熱して再生する
に際して、その貫通孔を再生炉における空気流と平行と
なるようにハニカム触媒を再生炉に装填すれば、空気の
圧力損失が大きく、触媒の再生効率が低くならざるを得
ないが、本発明によれば、ハニカム触媒の複数をその貫
通孔が上記再生炉における上記空気流に対して垂直とな
るように装填して、空気をハニカム触媒の間の空隙を流
れさせるので、空気の圧力損失が小さく、触媒の再生効
率を高くすることができる。従って、ハニカム触媒の間
の空隙、即ち、間隔は、再生炉内において、加熱した空
気が十分な線速を有する程度であればよく、特に、限定
されるものではない。When the honeycomb catalyst is regenerated by heating with air, if the honeycomb catalyst is loaded into the regenerating furnace so that its through-holes are parallel to the air flow in the regenerating furnace, the pressure loss of the air is large, and Although the regeneration efficiency must be low, according to the present invention, a plurality of honeycomb catalysts are loaded so that the through holes thereof are perpendicular to the air flow in the regeneration furnace, and the air is supplied to the honeycomb catalysts. Since the gaps are caused to flow, the pressure loss of air is small, and the regeneration efficiency of the catalyst can be increased. Therefore, the space between the honeycomb catalysts, that is, the space is not particularly limited as long as the heated air has a sufficient linear velocity in the regeneration furnace.
【００２０】しかしながら、本発明によれば、このよう
に、貫通孔が再生炉における空気流に対して垂直となる
ように複数のハニカム触媒を再生炉内に装填し、ハニカ
ム触媒の間の空隙に加熱空気を流通させて、ハニカム触
媒をその端面からの加熱によって再生するので、ハニカ
ム触媒は、上記貫通孔の方向の触媒の長さ、即ち、その
厚さが５〜１００ｍｍの範囲にあることが好ましく、特
に、５〜５０ｍｍの範囲にあることが好ましい。However, according to the present invention, a plurality of honeycomb catalysts are loaded into the regenerating furnace such that the through holes are perpendicular to the air flow in the regenerating furnace, and the gaps between the honeycomb catalysts are filled in the gaps between the honeycomb catalysts. Since the honeycomb catalyst is regenerated by heating from the end face by flowing the heated air, the honeycomb catalyst may have a length of the catalyst in the direction of the through-hole, that is, a thickness in a range of 5 to 100 mm. Preferably, it is particularly preferably in the range of 5 to 50 mm.
【００２１】このように、本発明によれば、触媒上に付
着、蓄積した種々の有機物を温度別に分別揮散させるこ
とによって、それら有機物の燃焼を招くことなく、触媒
を再生することができるように、再生炉における空気の
加熱速度と線速を適切に制御することが重要である。即
ち、本発明によれば、再生炉にハニカム触媒を装填した
後、再生炉における空気の線速度を３ｍ／秒以上、好ま
しくは、３〜２０ｍ／秒、好ましくは、４〜１０ｍ／秒
の範囲となるように供給しながら、空気を５０℃／時以
下、好ましくは、１５〜５０℃／時、特に、好ましく
は、２０〜４０℃／時の加熱速度で加熱し、最終的に加
熱空気を１５０〜３５０℃、好ましくは、１８０〜２５
０℃の範囲の最終再生温度まで加熱した後、空気をこの
最終再生温度の範囲に保持して、適宜時間、再生炉に流
通させる。本発明によれば、このように、空気を所定の
加熱速度で加熱しつつ、これを再生炉に流通させること
によって、触媒上に付着、蓄積されている有機物を燃焼
させることなく、触媒から蒸発、揮散させることによっ
て再生するのである。As described above, according to the present invention, the various organic substances deposited and accumulated on the catalyst are separated and volatilized according to the temperature, so that the catalyst can be regenerated without causing the combustion of the organic substances. It is important to properly control the heating speed and the linear speed of the air in the regeneration furnace. That is, according to the present invention, after the honeycomb catalyst is loaded in the regeneration furnace, the linear velocity of air in the regeneration furnace is 3 m / sec or more, preferably 3 to 20 m / sec, preferably 4 to 10 m / sec. The air is heated at a heating rate of 50 ° C./hour or less, preferably 15 to 50 ° C./hour, particularly preferably 20 to 40 ° C./hour while finally supplying the heated air. 150-350 ° C, preferably 180-25
After heating to a final regeneration temperature in the range of 0 ° C., the air is kept in this final regeneration temperature range and circulated through the regeneration furnace for an appropriate time. According to the present invention, the air is heated at a predetermined heating rate and is passed through the regeneration furnace to evaporate from the catalyst without burning the organic substances attached and accumulated on the catalyst. It is regenerated by volatilizing.
【００２２】即ち、本発明によれば、触媒上に付着、蓄
積されている種々の有機物のうち、脂肪族アルコール類
やアルデヒド、ケトン類は、比較的低温（１００〜１５
０℃程度）で蒸発、揮散するので、先ず、空気を上記加
熱速度で加熱しながら、上記線速度で再生炉に供給する
ことによって、触媒を比較的低い温度において、ある時
間にわたって加熱して、上記脂肪族アルコール類やアル
デヒド類やケトン類を触媒から蒸発、揮散させ、次い
で、空気を最終再生温度（好ましくは、１８０〜２５０
℃程度）にまで前記加熱速度で加熱しつつ、上記線速度
で再生炉に供給することによって、触媒を上記高温にお
いて、ある時間にわたって加熱して、前記脂肪酸を触媒
から蒸発、揮散させて、触媒を再生するのである。That is, according to the present invention, among various organic substances adhered and accumulated on the catalyst, aliphatic alcohols, aldehydes and ketones are relatively low in temperature (100 to 15).
(About 0 ° C.), the catalyst is heated at a relatively low temperature for a certain period of time by supplying the air to the regenerating furnace at the above linear speed while heating the air at the above heating rate. The aliphatic alcohols, aldehydes and ketones are evaporated and volatilized from the catalyst, and then the air is heated to a final regeneration temperature (preferably 180 to 250).
(About ° C) to the regeneration furnace at the above-mentioned linear velocity while heating at the above-mentioned heating rate, thereby heating the catalyst at the above-mentioned high temperature for a certain time to evaporate and volatilize the above-mentioned fatty acid from the catalyst. To play.
【００２３】本発明によれば、このように、ハニカム触
媒を装填した再生炉にその加熱速度と線速とを適切に制
御しながら、空気を流通させて、使用済みの触媒を加熱
することによって、触媒上に付着し、蓄積されている種
々の有機物を温度別に分別揮散させて、触媒を再生す
る。According to the present invention, as described above, by heating the used catalyst by flowing air while appropriately controlling the heating speed and the linear speed in the regeneration furnace loaded with the honeycomb catalyst. Then, various organic substances adhering and accumulating on the catalyst are separated and evaporated at different temperatures to regenerate the catalyst.
【００２４】再生炉に供給する加熱空気の加熱速度が１
５℃／時よりも遅いときは、触媒の再生に徒に長時間を
必要とし、他方、５０℃／時よりも早いときは、加熱空
気の線速を高めても、上記有機物が触媒上で燃焼する。
また、線速の観点からみれば、線速が３ｍ／秒よりも小
さいときは、再生炉に供給する加熱空気の加熱速度を十
分小さくしても、上記有機物が触媒上で燃焼し、また、
加熱速度が小さいことから、触媒の再生が効率に欠け
る。しかし、２０ｍ／秒よりも大きくするには、非常に
大容量の送風装置と大型の加熱装置とを必要としなが
ら、エネルギー損失も徒に大きく、処理費用も著しく高
くなって、実用性がなくなる。The heating rate of the heating air supplied to the regeneration furnace is 1
When the temperature is lower than 5 ° C./hour, the regeneration of the catalyst requires a prolonged period. On the other hand, when the speed is higher than 50 ° C./hour, even if the linear velocity of the heated air is increased, the organic matter is not removed on the catalyst. Burn.
Further, from the viewpoint of the linear velocity, when the linear velocity is lower than 3 m / sec, even if the heating rate of the heating air supplied to the regeneration furnace is sufficiently reduced, the organic matter burns on the catalyst, and
Due to the low heating rate, catalyst regeneration is inefficient. However, if the speed is higher than 20 m / sec, a very large capacity air blower and a large heating device are required, but the energy loss is unnecessarily large, the processing cost is significantly increased, and practicality is lost.
【００２５】特に、実用性の観点からは、本発明によれ
ば、再生炉における線速度を４〜１０ｍ／秒の範囲とな
るように供給しながら、空気を２０〜４０℃／時の加熱
速度で加熱し、最終的に加熱空気を１８０〜２５０℃の
最終再生温度まで加熱し、この最終再生温度で適宜時
間、再生炉に流通させることが好ましい。加熱空気によ
る触媒の最終再生温度に加熱する時間は、加熱空気の加
熱速度や線速にもよるので、触媒が実質的に当初の活性
を有するまでの時間であればよく、このような時間は、
実験的に容易に定めることができる。しかし、通常は、
１０分程度から１時間程度である。In particular, from the viewpoint of practicality, according to the present invention, air is supplied at a heating rate of 20 to 40 ° C./hour while supplying a linear velocity in the regeneration furnace in a range of 4 to 10 m / sec. , And finally the heated air is heated to a final regeneration temperature of 180 to 250 ° C, and is preferably passed through the regeneration furnace at the final regeneration temperature for an appropriate time. The time for heating the catalyst to the final regeneration temperature by the heated air depends on the heating rate and the linear velocity of the heated air, and thus may be a time until the catalyst substantially has the initial activity. ,
It can be easily determined experimentally. But usually,
It takes about 10 minutes to 1 hour.
【００２６】図２は、再生炉に供給する空気の加熱の態
様を示す。空気の加熱速度が容易に理解できるように、
便宜上、温度の原点を０℃としてあるが、空気の最初の
温度が０℃に限定される趣旨ではない。FIG. 2 shows a mode of heating the air supplied to the regeneration furnace. To make it easier to understand the heating rate of air,
Although the origin of the temperature is set to 0 ° C. for convenience, the initial temperature of the air is not limited to 0 ° C.
【００２７】実用的には、例１に示すように、最初、即
ち、通常は室温から、最終再生温度まで実質的に一定の
速度で空気を加熱するのが好ましい。しかし、例２に示
すように、例えば、空気を１００℃まで比較的急速に加
熱し、１００℃で適宜時間、保持した後、１５０℃まで
比較的急速に加熱し、この温度で適宜時間保持し、この
後、最終再生温度である２００℃まで比較的急速に加熱
し、この温度で適宜時間保持してもよい。本発明によれ
ば、このように、空気の加熱温度を段階的に高めてよい
が、この場合も、途中での空気の加熱速度は、５０℃／
時以下とすることが必要である。In practice, as shown in Example 1, it is preferred to heat the air at a substantially constant rate from the beginning, usually from room temperature, to the final regeneration temperature. However, as shown in Example 2, for example, air is heated relatively quickly to 100 ° C. and held at 100 ° C. for an appropriate time, and then heated relatively quickly to 150 ° C. and held at this temperature for an appropriate time. Thereafter, heating may be performed relatively quickly to 200 ° C., which is the final regeneration temperature, and the temperature may be appropriately maintained at this temperature. According to the present invention, as described above, the heating temperature of the air may be increased stepwise, but also in this case, the heating rate of the air in the middle is 50 ° C. /
Hour or less.
【００２８】また、触媒の加熱初期、特に、空気温度が
８０〜１２０℃程度に達するまでは、空気の加熱速度が
５０℃／時を越えても、触媒上の有機物は燃焼すること
がないので、図２中、例３に示すように、必要に応じ
て、８０〜１２０℃程度の範囲の温度まで、急速に加熱
し、その後、前記線速を有するように、空気を再生炉に
流通させつつ、前記加熱速度で空気を加熱してもよい。
この方法によれば、触媒の再生に要する時間を短縮し
て、再生の効率を一層高めることができる。Also, since the organic matter on the catalyst does not burn even at the initial heating of the catalyst, particularly until the air temperature reaches about 80 to 120 ° C., even if the air heating rate exceeds 50 ° C./hour. In FIG. 2, as shown in Example 3, if necessary, the mixture is rapidly heated to a temperature in the range of about 80 to 120 ° C., and then the air is passed through the regeneration furnace so as to have the linear velocity. Alternatively, the air may be heated at the heating rate.
According to this method, the time required for regeneration of the catalyst can be shortened, and the regeneration efficiency can be further increased.
【００２９】本発明においては、再生炉に流通させる空
気の量と温度とを適切に制御するために、必要に応じ
て、バルブ１２を開いて、管系に新鮮な空気を補充し、
また、必要に応じて、バルブ１３を制御して、空気の一
部を外部に排出してもよい。しかしながら、補充する空
気量と排出する空気量を最小限に抑えつつ、空気を加熱
装置で加熱する際に、触媒から蒸発、揮散した有機物を
燃焼させることによって、それら有機物を外部に排出す
ることなく、触媒の再生を実質的にクローズド・システ
ムにて行なうことができる。In the present invention, in order to appropriately control the amount and temperature of the air flowing through the regeneration furnace, the valve 12 is opened as necessary to supply fresh air to the pipe system.
If necessary, the valve 13 may be controlled to discharge a part of the air to the outside. However, while minimizing the amount of air to be replenished and the amount of air to be discharged, when heating the air with a heating device, the organic matter evaporated and volatilized from the catalyst is burned, so that the organic matter is not discharged to the outside. The regeneration of the catalyst can be carried out in a substantially closed system.
【００３０】本発明において、オゾン脱臭触媒は、二酸
化マンガンを主成分とするものであれば、特に、限定さ
れるものではないが、通常、オゾン脱臭触媒は、二酸化
マンガン３０〜７０重量％と、酸化チタン、シリカ、ア
ルミナ、又はこれらの複合酸化物７０〜３０重量％とか
らなり、場合によっては、上記成分以外に芳香族ポリア
ミド繊維のような補強材を含んでいる。In the present invention, the ozone deodorizing catalyst is not particularly limited as long as it is mainly composed of manganese dioxide. Usually, however, the ozone deodorizing catalyst contains 30 to 70% by weight of manganese dioxide, It is composed of 70 to 30% by weight of titanium oxide, silica, alumina, or a composite oxide thereof, and in some cases, contains a reinforcing material such as aromatic polyamide fiber in addition to the above components.
【００３１】[0031]
【発明の効果】本発明によれば、以上のように、オゾン
脱臭処理に用いて、その上に有機物が付着し、蓄積し
て、活性が低下し、また、悪臭を有するに至った使用済
みのマンガンを主成分とするハニカム触媒を再生するに
際して、その貫通孔が空気流に対して垂直となると共
に、ハニカム触媒がその間に相互に空隙を有するように
順序よく、その複数を再生炉内に装填し、この再生炉に
線速度と加熱速度を適切に制御しながら、加熱した空気
を流通させ、このように、触媒を加熱した空気にて加熱
しながら、触媒上の前記有機物を分別蒸発し、揮散させ
ることによって、有機物の燃焼を招くことなく、使用済
みの触媒を当初の活性を有するまでに、しかも、無臭の
ものに効率的に再生することができる。According to the present invention, as described above, the organic substances adhere to and accumulate on the ozone deodorizing treatment, the activity is reduced, and the used odor is reduced. When regenerating a honeycomb catalyst containing manganese as a main component, the through-holes are perpendicular to the air flow, and the honeycomb catalysts are loaded in the regeneration furnace in order such that the honeycomb catalyst has a gap therebetween. Then, while appropriately controlling the linear velocity and the heating rate in the regeneration furnace, the heated air is allowed to flow, and thus the organic matter on the catalyst is separated and evaporated while heating the catalyst with the heated air, By volatilizing, the used catalyst can be efficiently regenerated to an odorless one until the used catalyst has the initial activity without causing combustion of organic substances.
【００３２】[0032]
実施例１〜１２及び比較例１〜４ 居住環境において、オゾンによる脱臭処理に用いて、そ
の上に有機物が付着し、蓄積して、活性の低下した使用
済みのハニカム触媒（２３０ｍｍ四方、厚さ１２ｍｍ）
を準備した。このオゾン脱臭触媒は、二酸化マンガン７
０重量％とシリカ・アルミナ複合酸化物３０重量％とか
らなる。これらの触媒から適宜数のサンプルを抽出し、
その臭いとオゾン分解率を調べたところ、使用前は、悪
臭がなく、また、オゾン分解率は平均で９9.９％であっ
たが、使用済み後は、悪臭を有し、オゾン分解率は平均
で７8.５％であった。Examples 1 to 12 and Comparative Examples 1 to 4 In a living environment, a used honeycomb catalyst (230 mm square, having a thickness of 230 mm, with a reduced activity, used for deodorization treatment with ozone, on which organic substances adhere, accumulate, and accumulate. 12mm)
Was prepared. This ozone deodorizing catalyst is composed of manganese dioxide 7
It consists of 0% by weight and 30% by weight of a silica / alumina composite oxide. Extract an appropriate number of samples from these catalysts,
When the odor and the ozone decomposition rate were examined, there was no odor before use and the ozone decomposition rate was 99.9% on average, but after use, it had a bad odor and the ozone decomposition rate was The average was 78.5%.
【００３３】触媒のオゾン分解率は次のようにして測定
した。触媒を反応器に据え付け、これにオゾン発生器か
らオゾン１ｐｐｍを含む空気を温度２０℃で空間速度１
０００００ｈｒ-1で供給し、反応器入口及び出口におけ
る空気中のオゾン濃度をオゾン分析計にて測定して、オ
ゾン分解率＝〔（反応器入口のオゾン濃度−反応器出口
のオゾン濃度）／（反応器入口のオゾン濃度）〕×１０
０（％）から求めた。The ozonolysis rate of the catalyst was measured as follows. A catalyst was installed in the reactor, and air containing 1 ppm of ozone was supplied from an ozone generator at a temperature of 20 ° C. and a space velocity of 1
The reactor was supplied at 00000 hr -1 , and the ozone concentration in the air at the inlet and outlet of the reactor was measured by an ozone analyzer. Ozone decomposition rate = [(ozone concentration at reactor inlet−ozone concentration at reactor outlet) / ( Ozone concentration at reactor inlet)] × 10
It was determined from 0 (%).
【００３４】上記使用済みの触媒２７０枚をその間に１
ｃｍの空隙を有するように順序よく、再生炉内に装填
し、表２に示すように、再生炉内の空気の線速と再生炉
内における空気の加熱速度を制御しながら、最終再生温
度２００℃まで空気を加熱し、この温度で触媒を１時間
加熱した後、再生炉に室温の空気を流通させて触媒を冷
却した。270 sheets of the used catalyst are put between
cm in order so as to have an air gap in the regeneration furnace, and as shown in Table 2, while controlling the linear velocity of air in the regeneration furnace and the heating rate of air in the regeneration furnace, the final regeneration temperature was 200 ° C. After heating the catalyst at this temperature for 1 hour, the catalyst was cooled by flowing air at room temperature through the regeneration furnace.
【００３５】このようにして再生した触媒のオゾン分解
率を表２に示すと共に、触媒再生の間に触媒上で有機物
が燃焼した触媒の枚数と、再生後の触媒が臭いを有する
かどうかをパネリストによる官能試験によって調べた。
結果を表２に示す。The ozone decomposition rate of the catalyst thus regenerated is shown in Table 2, and the number of catalysts in which organic substances burned on the catalyst during the regeneration of the catalyst and whether or not the regenerated catalyst has an odor were determined by a panelist. Was examined by a sensory test according to
Table 2 shows the results.
【００３６】[0036]
【表２】 [Table 2]
【００３７】本発明によれば、触媒の再生中に実質的に
有機物の燃焼なしに、当初のオゾン分解率を有し、且
つ、無臭の触媒を再生することができる。According to the present invention, it is possible to regenerate an odorless catalyst having an initial ozone decomposition rate without substantially burning organic substances during the regeneration of the catalyst.
【図１】は、本発明の方法を実施するのに好適な装置構
成の一例を示す。FIG. 1 shows an example of an apparatus configuration suitable for carrying out the method of the present invention.
【図２】は、本発明の方法において、再生炉に供給する
空気の加熱例を示す時間−温度グラフである。FIG. 2 is a time-temperature graph showing an example of heating air supplied to a regeneration furnace in the method of the present invention.
【符号の説明】 １…再生炉、２…再生炉への空気入口、３…再生炉から
の空気出口、４…空気加熱装置（バーナー）、５…送風
装置、６…再生炉内におけるハニカム触媒の間の空隙、
７…ハニカム触媒、８…管系、９…再生炉における空気
流、１０…温度計、１１…制御装置、１２、１３…バル
ブ。[Description of Signs] 1 ... regenerator, 2 ... air inlet to regenerator, 3 ... air outlet from regenerator, 4 ... air heating device (burner), 5 ... blower, 6 ... honeycomb catalyst in regenerator The gap between
7 Honeycomb catalyst, 8 Tube system, 9 Air flow in regeneration furnace, 10 Thermometer, 11 Controller, 12, 13 Valve.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 池田 城二 大阪府堺市戎島町５丁１番地 堺化学工業 株式会社内 (72)発明者 竹口 克也 大阪府堺市戎島町５丁１番地 堺化学工業 株式会社内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Joji Ikeda 5-1-1 Ebisshima-cho, Sakai City, Osaka Sakai Chemical Industry Co., Ltd. (72) Katsuya Takeguchi 5-1-1 Ebisshima-cho, Sakai City, Osaka Sakai Chemical Industrial Co., Ltd.
Claims (3)
有機物が付着し、蓄積して、活性の低下したマンガンを
主成分とするハニカム触媒の再生方法において、空気入
口と出口とを備えた再生炉に、上記ハニカム触媒の貫通
孔が上記再生炉における上記空気流に対して垂直となる
と共に、ハニカム触媒がその間に相互に空隙を有するよ
うにその複数を装填し、上記再生炉に空気を上記ハニカ
ム触媒の間の空隙における線速度が３ｍ／秒以上となる
ように供給しながら、空気を５０℃／時以下の加熱速度
で１５０〜３５０℃の最終再生温度まで加熱し、この温
度で上記ハニカム触媒が活性を回復するに足る時間、上
記加熱空気で加熱し、このように、触媒を加熱した空気
で加熱しながら、触媒から上記有機物を蒸発、揮散させ
ることを特徴とする触媒の再生方法。1. A method for regenerating a honeycomb catalyst containing manganese as a main component, in which an organic substance adheres and accumulates on a deodorizing treatment with ozone and has a reduced activity, the method comprising an air inlet and an outlet. In the regeneration furnace, a plurality of the honeycomb catalysts are loaded so that the through holes of the honeycomb catalyst are perpendicular to the air flow in the regeneration furnace, and the honeycomb catalysts have a gap therebetween, and air is supplied to the regeneration furnace. Air is heated at a heating rate of 50 ° C./hour or less to a final regeneration temperature of 150 to 350 ° C. while supplying the linear velocity in the gap between the honeycomb catalysts to be 3 m / sec or more. The honeycomb catalyst is heated with the heated air for a time sufficient to recover the activity, and the organic matter is evaporated and volatilized from the catalyst while heating the catalyst with the heated air. Method for regenerating the catalyst.
ｍｍ以下である請求項１に記載の触媒の再生方法。2. The thickness of the honeycomb catalyst in the through hole direction is 100.
The method for regenerating a catalyst according to claim 1, wherein the diameter is not more than mm.
炉からの排出空気を加熱して、再度、再生炉に供給する
際に、上記有機物を燃焼させる請求項１に記載の触媒の
再生方法。3. The method for regenerating a catalyst according to claim 1, wherein the air discharged from the regeneration furnace containing the organic matter evaporated and volatilized from the catalyst is heated, and the organic matter is burned when the air is supplied again to the regeneration furnace. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14383297A JP3918231B2 (en) | 1997-06-02 | 1997-06-02 | Catalyst regeneration method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14383297A JP3918231B2 (en) | 1997-06-02 | 1997-06-02 | Catalyst regeneration method |
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| Publication Number | Publication Date |
|---|---|
| JPH10328568A true JPH10328568A (en) | 1998-12-15 |
| JP3918231B2 JP3918231B2 (en) | 2007-05-23 |
Family
ID=15347991
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008073665A (en) * | 2006-09-25 | 2008-04-03 | Takuma Co Ltd | Catalyst regeneration method and regeneration facility |
| JP2010058067A (en) * | 2008-09-04 | 2010-03-18 | Takuma Co Ltd | Method for regenerating denitration catalyst, unit for regenerating denitration catalyst and apparatus for treating exhaust gas by using the unit |
| KR101390449B1 (en) * | 2010-04-30 | 2014-04-30 | 아사히 가세이 케미칼즈 가부시키가이샤 | Apparatus for removing substances from catalyst surface |
| WO2022102810A1 (en) * | 2020-11-12 | 2022-05-19 | Purespace Inc. | Catalytic activity recovery method of manganese oxide catalyst |
-
1997
- 1997-06-02 JP JP14383297A patent/JP3918231B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008073665A (en) * | 2006-09-25 | 2008-04-03 | Takuma Co Ltd | Catalyst regeneration method and regeneration facility |
| JP2010058067A (en) * | 2008-09-04 | 2010-03-18 | Takuma Co Ltd | Method for regenerating denitration catalyst, unit for regenerating denitration catalyst and apparatus for treating exhaust gas by using the unit |
| KR101390449B1 (en) * | 2010-04-30 | 2014-04-30 | 아사히 가세이 케미칼즈 가부시키가이샤 | Apparatus for removing substances from catalyst surface |
| WO2022102810A1 (en) * | 2020-11-12 | 2022-05-19 | Purespace Inc. | Catalytic activity recovery method of manganese oxide catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3918231B2 (en) | 2007-05-23 |
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