JP2015174017A - Acceleration of ozone oxidation reaction using transition metal-containing oxide porous body - Google Patents
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本発明は大気汚染防止法で排出規制が強化されつつある揮発性有機化合物（ＶＯＣ）の処理、悪臭防止法で排出規制が強化されつつある悪臭処理、農作物鮮度保持に当たってのエチレン、アルデヒド、テルペンの除去にあたって、遷移金属含有多孔質体上でオゾンとＶＯＣの酸化反応が促進される現象を利用して、大風量、低濃度のＶＯＣを処理する方法に関する。 The present invention relates to treatment of volatile organic compounds (VOC) whose emission regulations are being tightened by the Air Pollution Control Law, malodor treatment whose emission regulations are being strengthened by the Malodor Control Law, and ethylene, aldehydes, and terpenes for maintaining the freshness of crops. The present invention relates to a method for treating a large amount of VOC at a low concentration using a phenomenon in which an oxidation reaction between ozone and VOC is promoted on a transition metal-containing porous body.
ＶＯＣを含有する排ガス処理に於いて最も頻繁に採用されている方法は、排ガスに含まれるＶＯＣを高シリカゼオライトを充填した吸着塔に供給してＶＯＣを吸着除去し，ＶＯＣを吸着した高シリカゼオライト吸着塔に高温熱風を供給してＶＯＣを高温脱着させ、減容濃縮して脱着したＶＯＣを触媒燃焼で酸化分解するハニカムローターＴＳＡ＋触媒燃焼である。又今後普及が予想されるものとしては米国環境保護局（ＥＰＡ）が提案している強誘電体（チタン酸バリウム等）の充填塔において強誘電体表面で延命放電を行い、ここにＶＯＣ含有ガスを供給することで酸化分解する充填塔プラズマ処理 （Ｐａｃｋｅｄ Ｂｅｄ Ｐｌａｓｍａ ＶＯＣ Ｔｒｅａｔｍｅｎｔ）がある。これらの方法はＶＯＣの処理に対し一定の性能を示しているが、ハニカムローターＴＳＡ＋触媒燃焼では装置の複雑さと操作の煩雑さによるコスト低減の限界があり、充填塔プラズマ処理ではＶＯＣ除去率に限界があり今後のＶＯＣ排出規制に対応できない懸念がある。 The most frequently used method for treating exhaust gas containing VOC is to supply VOC contained in the exhaust gas to an adsorption tower packed with high silica zeolite to adsorb and remove VOC, and to adsorb VOC. This is honeycomb rotor TSA + catalyst combustion in which high-temperature hot air is supplied to the adsorption tower to desorb VOC at a high temperature, and the desorbed VOC is oxidized and decomposed by catalytic combustion. Also expected to be widely used in the future is a life extension discharge on the surface of a ferroelectric (barium titanate, etc.) packed by the US Environmental Protection Agency (EPA). There is a packed tower plasma treatment (Packed Bed Plasma VOC Treatment) in which oxidative decomposition is performed by supplying. These methods show a certain level of performance for VOC processing, but honeycomb rotor TSA + catalyst combustion has limitations in terms of cost reduction due to the complexity of the equipment and the complexity of operation, and the VOC removal rate is limited in packed tower plasma processing. There is a concern that it will not be able to meet future VOC emission regulations.
ＶＯＣ含有ガスにオゾンを加えてＶＯＣの均一気相反応による酸化分解をすることも考えられるが、低濃度ＶＯＣに対するオゾン酸化反応が遅いこと、未反応オゾンの処理が煩雑なこと、酸化剤として使用するオゾンの製造コストが高価なことから実用化には至っていない。又オゾン酸化反応の反応効率の向上のためＶＯＣおよびオゾンを高シリカゼオライトに吸着して、ＶＯＣおよびオゾンを共吸着して高シリカゼオライト結晶内でオゾンによるＶＯＣのオゾンによる酸化反応の高効率化を計ることが提案されている。この方法においてオゾン反応の高効率化は実現するが、ＶＯＣの反応が途中で停止して有機酸が生成して臭気成分になることおよびこの有機酸がゼオライト結晶に蓄積してオゾン酸化反応の反応速度が低下する課題がある。 Ozone can be added to the VOC-containing gas for oxidative decomposition by homogeneous gas phase reaction of VOC, but the ozone oxidation reaction to low concentration VOC is slow, the treatment of unreacted ozone is complicated, and it is used as an oxidizing agent Since the production cost of ozone is high, it has not been put into practical use. In order to improve the reaction efficiency of ozone oxidation reaction, VOC and ozone are adsorbed on high silica zeolite, and VOC and ozone are co-adsorbed to increase the efficiency of oxidation reaction of ozone by VOC by ozone in the high silica zeolite crystal. It is proposed to measure. In this method, the efficiency of the ozone reaction is improved, but the VOC reaction stops in the middle of the process, and an organic acid is generated and becomes an odor component, and the organic acid accumulates in the zeolite crystal and reacts with the ozone oxidation reaction. There is a problem that speed decreases.
発明者等は気相でのオゾン−ＶＯＣ酸化反応試験を行う中で遷移金属を含有する多孔質体に、オゾンとＶＯＣ（アルコール、ケトン、エステル、エーテル、アルデヒド、芳香族等）が接触したあとＶＯＣがオゾンで高効率に酸化され、未反応なオゾンは酸素に変換することを見いだした。すなわち
[１] ＶＯＣを含有するガスをオゾンと混合した後、遷移金属含有酸化物多孔質体と接触させて、ＶＯＣとオゾンの促進酸化で、ＶＯＣの高効率な分解を行なうことを特長とするＶＯＣのオゾン酸化反応方法。
[２] 前記ＶＯＣオゾン酸化反応用遷移金属含有酸化物多孔質体としてＣｏ、Ｍｎ、Ｃｕを含む酸化物を単独または複数から選択して調製する酸化物超微粒子を使用する、ＶＯＣのオゾン酸化反応方法。
[３] 前記[１]または[２]に記載のＶＯＣオゾン酸化反応用遷移金属含有酸化物の調整法として、Ｃｏ、Ｍｎ、Ｃｕの金属塩から１種類以上を選び混合水溶液を作り、アルカリ溶液と混合することにより沈殿物を生成させて濾過、水洗、乾燥した後、熱処理を施すことを特徴とする酸化物超微粒子の製造方法。
[４] 前記[１]に記載のＶＯＣを含有するガスをオゾンと混合する際、注入オゾン濃度と原料ＶＯＣ濃度（Ｃ１換算）の濃度比が０．８以上となるオゾン酸化反応方法。
[５] 前記[１]〜[３]のいずれかに記載のＶＯＣオゾン酸化反応用遷移金属含有酸化物において、ＢＥＴ比表面積が８０ｍ２以上である酸化物超微粒子粉末。
After the ozone and VOC (alcohol, ketone, ester, ether, aldehyde, aromatic, etc.) contacted the porous body containing the transition metal during the ozone-VOC oxidation reaction test in the gas phase. It was found that VOC was oxidized with ozone with high efficiency, and unreacted ozone was converted to oxygen. Ie
[1] A VOC characterized in that a VOC-containing gas is mixed with ozone and then brought into contact with a transition metal-containing oxide porous body to effect highly efficient decomposition of VOC by accelerated oxidation of VOC and ozone. Ozone oxidation reaction method.
[2] VOC ozone oxidation reaction using oxide ultrafine particles prepared by selecting one or more oxides containing Co, Mn, and Cu as the transition metal-containing oxide porous body for VOC ozone oxidation reaction Method.
[3] As a method for adjusting the transition metal-containing oxide for VOC ozone oxidation reaction according to [1] or [2], one or more metal salts of Co, Mn, and Cu are selected to form a mixed aqueous solution, and an alkaline solution A method for producing ultrafine oxide particles, wherein a precipitate is produced by mixing with water, filtered, washed with water, dried, and then subjected to heat treatment.
[4] An ozone oxidation reaction method in which, when the gas containing the VOC according to [1] is mixed with ozone, the concentration ratio between the injected ozone concentration and the raw material VOC concentration (converted to C1) is 0.8 or more.
[5] The oxide ultrafine particle powder having a BET specific surface area of 80 m 2 or more in the transition metal-containing oxide for VOC ozone oxidation reaction according to any one of [1] to [3].
本発明において、気相中のオゾン酸化分解反応に比べ、酸化反応速度が１０〜１００倍程度に達することが確認された。これは、気相に於いてはオゾンはＶＯＣ成分以外の第３物質との衝突により酸化分解に寄与することなく分解する頻度が多くなり、その効率はそれ程大きなものとはならない。一方、多孔質体内でのオゾンとＶＯＣ成分の酸化反応に於いては、遷移金属がオゾンで酸化状態となり、ここにＶＯＣ拡散して遷移金属を還元して、ＶＯＣは酸化する酸化−還元反応が進行していると推定している。この効率的なオゾンのＶＯＣの酸化のためのオゾンの消費量は、上記気相反応に比べ大幅に低減され且つ、顕著な反応速度の上昇が達成される。これは従来のオゾン酸化反応の知見においては何ら教示されていないものである。この性質を利用するとＶＯＣ処理に於けるオゾンの使用量を大幅に削減することが可能となる。 In the present invention, it was confirmed that the oxidation reaction rate reached about 10 to 100 times as compared with the ozone oxidative decomposition reaction in the gas phase. This is because, in the gas phase, ozone frequently decomposes without contributing to oxidative decomposition due to collision with a third substance other than the VOC component, and the efficiency is not so great. On the other hand, in the oxidation reaction of ozone and the VOC component in the porous body, the transition metal is oxidized by ozone, and VOC diffuses therein to reduce the transition metal, and the oxidation-reduction reaction in which VOC is oxidized. Presumed to be progressing. The consumption of ozone for this efficient ozone VOC oxidation is greatly reduced compared to the gas phase reaction and a significant increase in reaction rate is achieved. This is not taught at all in the knowledge of the conventional ozone oxidation reaction. Utilizing this property makes it possible to greatly reduce the amount of ozone used in the VOC treatment.
本発明の一実施態様を図−１に示す。１例として、ＶＯＣとしてＭＥＫ２５ｐｐｍを含有する排ガス１，０００ｍ３Ｎ／ｈを一流路通じて遷移金属多孔体充填塔３に供給する。遷移金属多孔体としては、Ｃｏ、Ｍｎ、Ｃｕ含有超微粒子酸化物、Ｃｏ含有超微粒子酸化物等が考えられる。これらのスラリーを、アルミナ、アルミナシリケート、シリカのコルゲートに担持して、乾燥、焼成してモノリスに成型して使用した。同時にオゾン発生機で発生したオゾンを他の流路から前述流路に結び、ＶＯＣと混合して、充填塔３に供給する。（充填塔には遷移金属多孔質体が充填されている。ここで入口オゾン濃度／入口ＶＯＣ濃度（Ｃ１換算）比を０．８以上、ＳＶ値（１ｍ３の充填塔当たりの処理ガス流量（ｍ３Ｎ／ｈ）、単位（１／ｈ））を、入口ＶＯＣ濃度１００ｐｐｍ（Ｃ１換算）でＳＶ値１０，０００以下、入口ＶＯＣ濃度１０ｐｐｍ（Ｃ１換算）でＳＶ値２５，０００以下、入口ＶＯＣ濃度１ｐｐｍ（Ｃ１換算）でＳＶ値５０，０００以下とすると供給されるＶＯＣの９０％以上が分解される。 One embodiment of the present invention is shown in FIG. As an example, an exhaust gas 1,000 m 3 N / h containing 25 ppm of MEK as VOC is supplied to the transition metal porous body packed tower 3 through one flow path. As the transition metal porous body, Co, Mn, Cu-containing ultrafine oxide, Co-containing ultrafine oxide, and the like can be considered. These slurries were supported on alumina, alumina silicate, and silica corrugates, dried, fired, and molded into a monolith for use. At the same time, the ozone generated by the ozone generator is connected from the other flow path to the flow path, mixed with VOC, and supplied to the packed tower 3. (The packed tower is filled with a transition metal porous body. Here, the inlet ozone concentration / inlet VOC concentration (C1 conversion) ratio is 0.8 or more and the SV value (processing gas flow rate per packed tower of 1 m 3 ( m 3 N / h), unit (1 / h)) at an inlet VOC concentration of 100 ppm (C1 conversion), an SV value of 10,000 or less, an inlet VOC concentration of 10 ppm (C1 conversion), an SV value of 25,000 or less, an inlet VOC If the SV value is 50,000 or less at a concentration of 1 ppm (C1 conversion), 90% or more of the supplied VOC is decomposed.
ＶＯＣとしてＭＥＫ２５ｐｐｍを含有する排ガス１，０００ｍ３Ｎ／ｈ １を流路２に通じて遷移金属多孔体充填塔３に供給する。遷移金属多孔体４としては、Ｓａｍｐｌｅ−ＡとしてＣｏ、Ｍｎ、Ｃｕ含有超微粒子酸化物を、Ｓａｍｐｌｅ−Ｂとしては、Ｃｏ含有超微粒子酸化物を調製した。 An exhaust gas 1,000 m 3 N / h 1 containing 25 ppm of MEK as VOC is supplied to the transition metal porous body packed tower 3 through the flow path 2. As the transition metal porous body 4, Co-, Mn, and Cu-containing ultrafine oxides were prepared as Sample-A, and Co-containing ultrafine oxides were prepared as Sample-B.
Ｓａｍｐｌｅ−Ａの調製は、Ｃｏ、Ｍｎ、Ｃｕの金属塩水溶液とアルカリ水溶液を水媒体中に滴下し、各金属の共沈物を析出させた。得られた共沈物を濾過、水洗、乾燥した後１００〜５００℃の範囲で熱処理を行い、目的とするＣｏ、Ｍｎ、Ｃｕ含有超微粒子酸化物を得た。この際に使用する各金属の塩は、市販の金属塩であればいずれも使用可能で、硫酸塩、硝酸塩、塩化物などが使用可能である。また使用するアルカリは苛性ソーダ、ソーダ゛灰、重曹などの一般的なアルカリが使用可能である。混合する金属塩の割合は各金属の全体に対するモル比でＣｏは４０モル％以下、Ｍｎは３０〜７０モル％、Ｃｕは２５〜４５モル％の範囲が好適である。また、金属塩の濃度は概ね５〜５０重量％の範囲が適当である。沈殿条件としては、沈殿ｐHは遷移金属が沈殿する範囲のｐH領域にあれば微細な沈殿が析出でき、概ね５〜１４の範囲が適当である。得られた沈殿物は無定形に近いが、結晶をより完全なものにするためには熱処理が必要で、１００〜５００℃の範囲が良好である。熱処理温度が高いと比表面積が減少し、ＶＯＣ吸着サイトが減少するため吸着特性が劣化する。 Sample-A was prepared by dropping a metal salt aqueous solution of Co, Mn, and Cu and an aqueous alkali solution into an aqueous medium to precipitate a coprecipitate of each metal. The obtained coprecipitate was filtered, washed with water and dried, and then subjected to a heat treatment in the range of 100 to 500 ° C. to obtain the intended Co, Mn, Cu-containing ultrafine oxide. Any metal salt can be used as long as it is a commercially available metal salt, and sulfates, nitrates, chlorides, and the like can be used. As the alkali to be used, general alkalis such as caustic soda, soda ash, and baking soda can be used. The ratio of the metal salt to be mixed is preferably in the range of 40 mol% or less, Co in the range of 30 to 70 mol%, and Cu in the range of 25 to 45 mol% with respect to the total amount of each metal. The concentration of the metal salt is generally in the range of 5 to 50% by weight. As the precipitation condition, if the precipitation pH is in the pH region where the transition metal is precipitated, a fine precipitate can be precipitated, and the range of about 5 to 14 is appropriate. The obtained precipitate is almost amorphous, but heat treatment is necessary to make the crystal more complete, and the range of 100 to 500 ° C. is good. When the heat treatment temperature is high, the specific surface area decreases and the VOC adsorption sites decrease, so that the adsorption characteristics deteriorate.
Ｓａｍｐｌｅ−Ｂの調整はＣｏの金属溶液とアルカリ水溶液を水媒体中に滴下し、Ｃｏ金属の沈殿物を得た。得られた沈殿物を濾過、水洗、乾燥した後３００〜８００℃の範囲で熱処理を行い、目的とするＣｏ含有微粒子酸化物を得た。この際に使用するＣｏ金属の塩は、市販の金属塩であればいずれも使用可能で、硫酸塩、硝酸塩、塩化物などが使用可能である。また使用するアルカリは苛性ソーダ、ソーダ゛灰、重曹などの一般的なアルカリが使用可能である。また金属塩の濃度は概ね５〜５０重量％の範囲が適当である。沈殿条件としては、沈殿ｐHはＣｏ金属が沈殿する範囲のｐH領域にあれば微細な沈殿が析出でき、概ね５〜１４の範囲が適当である。得られた沈殿物は無定形に近いが、一部結晶化しており、さらに結晶を完全なものにするためには熱処理が必要で、３００〜８００℃の範囲が良好である。熱処理温度が高いと比表面積が減少し、ＶＯＣ吸着サイトが減少するため吸着特性が劣化する。 For the adjustment of Sample-B, a Co metal solution and an alkaline aqueous solution were dropped into an aqueous medium to obtain a Co metal precipitate. The obtained precipitate was filtered, washed with water, and dried, and then heat-treated at a temperature in the range of 300 to 800 ° C. to obtain a target Co-containing fine particle oxide. Any Co metal salt can be used as long as it is a commercially available metal salt, and sulfates, nitrates, chlorides, and the like can be used. As the alkali to be used, general alkalis such as caustic soda, soda ash, and baking soda can be used. The concentration of the metal salt is generally in the range of 5 to 50% by weight. As the precipitation condition, if the precipitation pH is in the pH region where Co metal is precipitated, a fine precipitate can be precipitated, and a range of about 5 to 14 is appropriate. The obtained precipitate is almost amorphous, but is partially crystallized, and further heat treatment is necessary to complete the crystal, and the range of 300 to 800 ° C. is good. When the heat treatment temperature is high, the specific surface area decreases and the VOC adsorption sites decrease, so that the adsorption characteristics deteriorate.
上記記載の製造法によるＳａｍｐｌｅ−Ａ、Ｓａｍｐｌｅ−Ｂは各金属の酸化物や炭酸塩、塩基性炭酸塩、シュウ酸塩などを組み合わせて乾式混合し、焼成することにより製造が可能であるが、各金属の酸化物などの混合原料は１次粒子が大きく、焼成して得られる粉末の粒子径はサブミクロンが限界で、それ以下の粒子径を作ることは難しい。従って、比表面積も数ｍ２程度で、吸着サイトの少ない粉末になる。それに対し、上記記載の湿式法による粉末は場合により、１００ｍ２を超えるサンプルを作ることができるため、当該ＶＯＣ除去に極めて有用である。 Sample-A and Sample-B by the above-described production method can be produced by dry-mixing and firing oxides, carbonates, basic carbonates, oxalates and the like of each metal, A mixed raw material such as an oxide of each metal has large primary particles, and the particle size of the powder obtained by firing is limited to submicrons, and it is difficult to make a particle size smaller than that. Therefore, the specific surface area is about several m 2 and the powder has few adsorption sites. On the other hand, since the powder by the wet method described above can make a sample exceeding 100 m 2 in some cases, it is extremely useful for removing the VOC.
このようにして得られた超微粒子遷移金属酸化物を１０ｗ％のスラリーとして、アルミナシリケートで成型されたコルゲート（平板と波状板を交互に積層した基材（平板間隔２ｍｍ、波状板山−山間隔２ｍｍ、板厚０．２ｍｍ）に担持して、２５０℃で乾燥、焼成してモノリスに成型して使用した。また参照のために従来法であるゼオライトとしてＳｉＯ２／Ａｌ２Ｏ３比１００の超安定Ｙ型ゼオライト（ＵＳＹ）モノリスに成型して使用した。また同時にオゾン発生機５で発生したオゾン（最大５００ｇ／ｈｒ）を流路６から流路２に結び、ＶＯＣと混合して、充填塔３に供給する。（充填塔３は直径６０ｃｍ、高さ３０ｃｍの大きさでありここに８０Ｌの遷移金属多孔質体４が充填されている。（空塔速度は１ｍ／ｓｅｃ、ＳＶ値は１０，０００１／ｈで有る。）オゾン酸化分解後の排ガスは流路７から流過するので採取ライン８から排ガスを採取して反応生成物、未反応オゾン、未反応ＶＯＣの濃度計測を行い本発明の有効性を検証した。本発明の試験条件及び各種シリカ多孔質体のオゾン酸化分解特性を吸着工程出口ＭＥＫ濃度、Ｏ３濃度で評価したのでこれを表−１に示す。 The thus obtained ultrafine transition metal oxide was made into a slurry of 10 w%, and a corrugated substrate made of alumina silicate (a substrate in which flat plates and corrugated plates were alternately laminated (flat plate interval 2 mm, corrugated plate crest-crest interval) 2 mm, plate thickness 0.2 mm), dried and calcined at 250 ° C., molded into a monolith and used as a conventional zeolite for reference with a SiO 2 / Al 2 O 3 ratio of 100. Used by molding into ultra-stable Y-type zeolite (USY) monolith, and at the same time, ozone (maximum 500 g / hr) generated by the ozone generator 5 is connected from the flow path 6 to the flow path 2 and mixed with VOC for filling. It is supplied to the tower 3. (The packed tower 3 has a diameter of 60 cm and a height of 30 cm, and is filled with 80 L of the transition metal porous body 4. (The superficial velocity is 1 m / sec, the SV value is The exhaust gas after ozone oxidative decomposition flows from the flow path 7, so the exhaust gas is sampled from the sampling line 8, and the concentration of the reaction product, unreacted ozone and unreacted VOC is measured. The effectiveness of the invention was verified, and the test conditions of the present invention and the ozone oxidative decomposition characteristics of various porous silica materials were evaluated by the adsorption process outlet MEK concentration and O 3 concentration, which are shown in Table 1.
以下、本発明を実施例に基づいて具体的に説明する
表−１に基づき、遷移金属多孔体として、１：共沈法で調製したＣｏ、Ｍｎ、Ｃｕ酸化物を含有する超微粒子から構成される多孔質体モノリス（Ｓａｍｐｌｅ−Ａ）、２：沈殿法で調製したＣｏ酸化物を含有する超微粒子から構成される多孔質体モノリス（Ｓａｍｐｌｅ−Ｂ）、３：参照として公知多孔質体として超安定Ｙ型ゼオライト（ＵＳＹ）（Ｓａｍｐｌｅ−Ｃ）からなるモノリスを充填塔に充填して、ＶＯＣのオゾン酸化反応による分解性能を評価した。
試験では、１）入口ガス量／充填塔体積比（ＳＶ値（１／ｈｒ）、２）入口オゾン濃度／入口ＭＥＫ濃度（Ｃ１換算）比、３）入口オゾン濃度（Ｃ１換算）を変更して、Ａ）ＭＥＫの流過率（ＭＥＫ出口／入口濃度比）、Ｂ）オゾン流過率（オゾン出口／入口濃度比）で評価した。
Hereinafter, based on Table-1 which demonstrates this invention concretely based on an Example, it is comprised from the ultrafine particle containing Co, Mn, and Cu oxide prepared by 1: coprecipitation method as a transition metal porous body. Porous monolith (Sample-A), 2: Porous monolith (Sample-B) composed of ultrafine particles containing Co oxide prepared by the precipitation method, 3: As a known porous body A monolith made of stable Y-type zeolite (USY) (Sample-C) was packed in a packed tower, and the decomposition performance of the VOC by the ozone oxidation reaction was evaluated.
In the test, 1) the inlet gas amount / packed tower volume ratio (SV value (1 / hr), 2) the inlet ozone concentration / inlet MEK concentration (C1 conversion) ratio, and 3) the inlet ozone concentration (C1 conversion) were changed. A) MEK flow rate (MEK outlet / inlet concentration ratio) and B) ozone flow rate (ozone outlet / inlet concentration ratio).
試験結果及び結果に基づく評価を表−２ａ、表−２ｂ、表−２ｃに示す。
表−２の試験条件でＲｕｎをハイフンで結ぶ３桁の数字で表したが、左端の数字が、１は、共沈法で調製したＣｏ、Ｍｎ、Ｃｕ含有酸化物超微粒子モノリスを表し、２は、沈殿法で調製したＣｏ含有酸化物超微粒子モノリスを表し、３は、ＵＳＹモノリスを表す。次に中央の数字が、１は、実験変数の入口ガス量の変更を表し、２は、入口オゾン量の変更を表し、３は、入口ＭＥＫ濃度の変更を表した。
右端の数字は、各モノリス、実験変数に於ける実験条件を表している。
この表記に基づき、Ｓａｍｐｌｅ−Ａの試験結果を表−２ａに記し、Ｓａｍｐｌｅ−Ｂの結果を表−２ｂ、Ｓａｍｐｌｅ−Ｃの結果を表−２ｃに記した。
Test results and evaluations based on the results are shown in Table-2a, Table-2b, and Table-2c.
In the test conditions shown in Table 2, the three-digit number connecting Run with hyphens, the leftmost number 1 represents a Co, Mn, Cu-containing oxide ultrafine monolith prepared by a coprecipitation method. Represents a Co-containing oxide ultrafine particle monolith prepared by a precipitation method, and 3 represents a USY monolith. Next, the central number 1 represents a change in the inlet gas amount as an experimental variable, 2 represents a change in the inlet ozone amount, and 3 represents a change in the inlet MEK concentration.
The numbers on the right end represent the experimental conditions for each monolith and experimental variable.
Based on this notation, the test results of Sample-A are shown in Table-2a, the results of Sample-B are shown in Table-2b, and the results of Sample-C are shown in Table-2c.
（入口ガス量依存性）
入口ガス量を、５，０００ｍ３Ｎ／ｈから２５０ｍ３Ｎ／ｈ迄変更すると、ＳＶ値は、６０，０００から３，０００に低下する。この時、Ｓａｍｐｌｅ−Ａでは、ＭＥＫ流過率は、３６％から１．２％に低下する。Ｓａｍｐｌｅ−Ｂでは、４３％から１．４％に変化し、Ｓａｍｐｌｅ−Ｃでは、６４．８％から５．４％に変化する。
Ｃｏ，Ｍｎ，Ｃｕ酸化物超微粒子（Ｓａｍｐｌｅ−Ａ）が最も良い性能を示し、Ｃｏ含有酸化物超微粒子（Ｓａｍｐｌｅ−Ｂ）がこれに続き、ＵＳＹ（Ｓａｍｐｌｅ−Ｃ）の性能はかなり低い。
(Depends on inlet gas amount)
When the inlet gas amount is changed from 5,000 m 3 N / h to 250 m 3 N / h, the SV value decreases from 60,000 to 3,000. At this time, in Sample-A, the MEK flow rate decreases from 36% to 1.2%. In Sample-B, it changes from 43% to 1.4%, and in Sample-C, it changes from 64.8% to 5.4%.
Co, Mn, Cu oxide ultrafine particles (Sample-A) show the best performance, followed by Co-containing oxide ultrafine particles (Sample-B), and the performance of USY (Sample-C) is considerably low.
（オゾン注入量依存性）
入口オゾン濃度/入口ＭＥＫ濃度（Ｃ１換算）比が１．３から０．８の間で変更するように、オゾンの注入量を、０．２７−０．１７ｋｇ／ｈの間で注入量を変更した。
Ｓａｍｐｌｅ−Ａでは、ＭＥＫ流過率は、４％から２０％に上昇する。このことから、入口オゾン濃度/入口ＭＥＫ濃度（Ｃ１換算）比は、１以上を保持することが必要であり、Ｃ１換算ＭＥＫ濃度に対応して、入口オゾン濃度/入口ＭＥＫ濃度（Ｃ１換算）比＞１での、オゾンの注入でＭＥＫ流過率１０％以下が達成できる。ここでも、ＭＥＫ分解性能は、Ｓａｍｐｌｅ−Ａ，Ｓａｍｐｌｅ−Ｂ，Ｓａｍｐｌｅ−Ｃの順で有り、ＵＳＹに比べ遷移金属多孔質体のＶＯＣ分解性能の顕著な優位性が確認できた。
(Dependence on ozone injection amount)
Change the injection amount of ozone between 0.27 and 0.17 kg / h so that the inlet ozone concentration / inlet MEK concentration (C1 conversion) ratio changes between 1.3 and 0.8. did.
In Sample-A, the MEK flow rate increases from 4% to 20%. Therefore, the inlet ozone concentration / inlet MEK concentration (C1 conversion) ratio needs to be maintained at 1 or more, and the inlet ozone concentration / inlet MEK concentration (C1 conversion) ratio corresponds to the C1 conversion MEK concentration. A MEK flow rate of 10% or less can be achieved by ozone injection at> 1. Here again, the MEK decomposition performance is in the order of Sample-A, Sample-B, and Sample-C, and it was confirmed that the VOC decomposition performance of the transition metal porous material was significantly superior to that of USY.
（ＭＥＫ濃度依存性）
入口ＭＥＫ濃度（Ｃ１換算）を１００から１ｐｐｍの間で変更して、ＭＥＫ流過率が１０％以下となる入口流量を調整した。
(MEK concentration dependency)
The inlet MEK concentration (C1 conversion) was changed between 100 and 1 ppm, and the inlet flow rate at which the MEK flow rate was 10% or less was adjusted.
Ｓａｍｐｌｅ−Ａを例にすると、ＭＥＫ濃度１００ｐｐｍでは、ＭＥＫ流過率１０％以下を確保できる、入口流量は１，０００ｍ３Ｎ／ｈ程度（ＳＶ１０，０００）である。ここでＭＥＫ濃度を１０ｐｐｍに下げると流過率１０％以下を確保できる流量は２，５００ｍ３Ｎ／ｈ程度（ＳＶ２５，０００）となり、ＭＥＫ濃度１ｐｐｍでは、入口ガス量５，０００ｍ３Ｎ／ｈ（ＳＶ５０，０００）でもＭＥＫ流過率１０％以下が達成できる。これから判るように、ＭＥＫ入口濃度が下がると、より大きなＳＶ値（少ない充填量）でＭＥＫ分解性能が達成できることが判る。ここでも、ＭＥＫ分解性能は、Ｓａｍｐｌｅ−Ａ，Ｓａｍｐｌｅ−Ｂ，Ｓａｍｐｌｅ−Ｃの順で有り、ＵＳＹに比べ遷移金属多孔質体のＶＯＣ分解性能の顕著な優位性が確認できた。 Taking Sample-A as an example, at an MEK concentration of 100 ppm, an MEK flow rate of 10% or less can be secured, and the inlet flow rate is about 1,000 m 3 N / h (SV10,000). Here, when the MEK concentration is lowered to 10 ppm, the flow rate at which a flow rate of 10% or less can be secured is about 2,500 m 3 N / h (SV25,000). When the MEK concentration is 1 ppm, the inlet gas amount is 5,000 m 3 N / h. Even with (SV50,000), a MEK flow rate of 10% or less can be achieved. As can be seen from this, when the MEK inlet concentration decreases, the MEK decomposition performance can be achieved with a larger SV value (small filling amount). Here again, the MEK decomposition performance is in the order of Sample-A, Sample-B, and Sample-C, and it was confirmed that the VOC decomposition performance of the transition metal porous material was significantly superior to that of USY.
（ＶＯＣの種類への汎用性）
入口ガス量を、１，０００ｍ３Ｎ／ｈ、ＳＶ値は、１２，０００、使用する遷移金属多孔質体は、ＭＥＫオゾン処理で最も良好なオゾン分解性能を示した、Ｃｏ，Ｍｎ，Ｃｕ系多孔質体のＳａｍｐｌｅ−Ａを充填し、注入オゾン濃度／ＶＯＣ濃度（Ｃ１換算）比１．２として、処理対象ＶＯＣとしてＭＥＫに替えて、１）酢酸エチル１００ｐｐｍ ａｓＣ１（２５ｐｐｍ ａｓ 酢酸エチル）、２）シクロヘキサノン１００ｐｐｍ ａｓＣ１（１６．６ｐｐｍ ａｓ シクロヘキサノン）、３）トルエン１００ｐｐｍ ａｓＣ１（１４．３ｐｐｍ ａｓ トルエン）、４）スチレン１００ｐｐｍ ａｓＣ１（１２．５ｐｐｍ ａｓ スチレン）、５）キシレン１００ｐｐｍ ａｓＣ１（１２．５ｐｐｍ ａｓ キシレン）、６）アセトアルデヒド１００ｐｐｍ ａｓＣ１（５０ｐｐｍ ａｓ アセトアルデヒド）、７）プロピオンアルデヒド５０ｐｐｍ ａｓＣ１（１６．６ｐｐｍ ａｓ プロピオンアルデヒド）、８）プロピオン酸５０ｐｐｍ ａｓＣ１（１６．６ｐｐｍ ａｓ プロピオン酸）、９）酢酸１５０ｐｐｍ ａｓＣ１（７５ｐｐｍ ａｓ 酢酸）のオゾン酸化処理を行った。この時の流過率は、１）酢酸エチル３％、２）シクロヘキサノン６％、３）トルエン８％、４）スチレン６％、５）キシレン５％、６）アセトアルデヒド１５％、７）プロピオンアルデヒド１０％、８）プロピオン酸４％、９）酢酸３％の良好な分解性能を示した。
(General versatility to VOC types)
Inlet gas amount is 1,000 m 3 N / h, SV value is 12,000, and the transition metal porous body to be used is the Co, Mn, Cu system that showed the best ozonolysis performance by MEK ozone treatment. Sample-A of a porous body is filled, and the injection ozone concentration / VOC concentration (C1 conversion) ratio is 1.2. Instead of MEK as the VOC to be treated, 1) ethyl acetate 100 ppm asC1 (25 ppm as ethyl acetate), 2 ) Cyclohexanone 100 ppm asC1 (16.6 ppm as cyclohexanone), 3) Toluene 100 ppm asC1 (14.3 ppm as toluene), 4) Styrene 100 ppm asC1 (12.5 ppm as styrene), 5) Xylene 100 ppm asC1 (12.5 ppm as xylene) 6) Acetaldehyde 100 ppm a C1 (50 ppm as acetaldehyde), 7) Propionaldehyde 50 ppm asC1 (16.6 ppm as propionaldehyde), 8) Propionic acid 50 ppm asC1 (16.6 ppm as propionic acid), 9) Acetic acid 150 ppm asC1 (75 ppm as acetic acid) ozone oxidation Processed. The flow rates at this time were as follows: 1) ethyl acetate 3%, 2) cyclohexanone 6%, 3) toluene 8%, 4) styrene 6%, 5) xylene 5%, 6) acetaldehyde 15%, 7) propionaldehyde 10 %, 8) propionic acid 4%, 9) acetic acid 3%.
（気相無機還元性化合物への適用）
入口ガス量を、１，０００ｍ３Ｎ／ｈ、ＳＶ値は、１２，０００、使用する遷移金属多孔質体は、ＶＯＣオゾン処理で最も良好なオゾン分解性能を示した、Ｃｏ、Ｍｎ、Ｃｕ系多孔質体のＳａｍｐｌｅ−Ａを充填し、注入オゾン濃度／気相無機還元性化合物濃度比２として、処理対象気相無機還元性化合物として、１）アンモニア１００ｐｐｍ、２）メチルメルカプタン１０ｐｐｍ、３）トリメチルアミン１００ｐｐｍ、４）硫化水素１０ｐｐｍ、５）一酸化炭素１０ｐｐｍのオゾン酸化処理を行った。この時１）アンモニア流過率は、０．５％、２）メチルメルカプタン流過率１％、３）トリメチルアミン流過率６％、４）硫化水素流過率１％、５）一酸化炭素流過率５％の良好な分解性能を示した。
このことから当該発明の適用により、オゾンに対して還元性化合物であるＶＯＣに対し従来全く示唆されなかった処理効率が示された。
(Application to gas phase inorganic reducing compounds)
The inlet gas amount is 1,000 m 3 N / h, the SV value is 12,000, and the transition metal porous body used has the best ozonolysis performance in the VOC ozone treatment. Sample-A of a porous body is filled, and the injection ozone concentration / gas phase inorganic reducing compound concentration ratio is 2, the gas phase inorganic reducing compound to be treated is 1) ammonia 100 ppm, 2) methyl mercaptan 10 ppm, 3) trimethylamine 100 ppm, 4) 10 ppm of hydrogen sulfide, and 5) ozone oxidation treatment of 10 ppm of carbon monoxide. At this time, the ammonia flow rate was 0.5%, 2) methyl mercaptan flow rate 1%, 3) trimethylamine flow rate 6%, 4) hydrogen sulfide flow rate 1%, and 5) carbon monoxide flow. Good decomposition performance with an excess rate of 5% was exhibited.
From this, application of the present invention showed a treatment efficiency that has never been suggested for VOC, which is a reducing compound for ozone.
本発明は大気汚染防止法で排出規制が強化されつつある揮発性有機化合物（ＶＯＣ）の処理、悪臭防止法で排出規制が強化されつつある悪臭処理、農作物鮮度保持に当たって障害因子となるエチレン、アルデヒド、テルペンの除去のための、大風量、回収するには低濃度のＶＯＣを処理への適用が期待される。 The present invention relates to treatment of volatile organic compounds (VOC) whose emission regulations are being tightened by the Air Pollution Control Law, malodor treatment whose emissions regulations are being tightened by the Malodor Control Law, and ethylene and aldehydes which are obstacles in maintaining the freshness of crops In order to recover terpene, it is expected to apply a large amount of air to the processing, and to recover VOC at a low concentration.
流路 ―――１、２ａ、２ｂ、２ｃ、２ｄ、５ａ、５ｂ、５ｃ、５ｄ、６、８、１１
吸着塔―――３ａ、３ｂ、３ｃ、３ｄ
トルエン吸着塔―――４ａ、４ｂ、４ｃ、４ｄ
オゾン発生器―――７
オゾン吸着反応器―――９
高シリカゼオライトハニカム―――１０
排ガス―――１
流路 ―――２、６、７
遷移金属多孔体充填塔―――３
遷移金属多孔体―――４
オゾン発生機―――５
採取ライン―――８
Flow path --- 1, 2a, 2b, 2c, 2d, 5a, 5b, 5c, 5d, 6, 8, 11
Adsorption tower--3a, 3b, 3c, 3d
Toluene adsorption tower--4a, 4b, 4c, 4d
Ozone generator--7
Ozone adsorption reactor --- 9
High silica zeolite honeycomb--10
Exhaust gas
Flow path ――― 2, 6, 7
Transition metal porous packed tower --- 3
Transition metal porous body --- 4
Ozone generator--5
Sampling line--8
Claims (5)
The VOC and / or gas phase inorganic reducing compound transition metal containing oxide for ozone oxidation reaction according to any one of claims 1 to 3, wherein the oxide ultrafine particle powder has a BET specific surface area of 80 m 2 or more.
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| WO2017056517A1 (en) * | 2015-09-30 | 2017-04-06 | 吸着技術工業株式会社 | Ozone oxidative decomposition treatment method for vocs and/or gaseous inorganic reducing compounds in gas |
| CN109414647A (en) * | 2016-10-07 | 2019-03-01 | 托普索公司 | It is a kind of for the clean method of cryogenic gas and for the catalyst of this method |
| US10493423B2 (en) | 2015-09-30 | 2019-12-03 | Futamura Kagaku Kabushiki Kaisha | Purification treatment method of liquid containing harmful substance, and purification treatment device of liquid containing harmful substance for carrying out said method |
| JP2020081934A (en) * | 2018-11-20 | 2020-06-04 | フタムラ化学株式会社 | Filter body used for ozone oxidization decomposition treatment, and production method of the same |
| CN114534662A (en) * | 2022-03-08 | 2022-05-27 | 昆明理工大学 | Method for removing organic matters in sodium aluminate solution by ultrasonic-heterogeneous catalytic ozonation |
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| CN114534662B (en) * | 2022-03-08 | 2024-01-30 | 昆明理工大学 | Method for removing organic matters in sodium aluminate solution by ultrasonic-heterogeneous catalytic ozonation |
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