JP4191906B2 - Metal honeycomb catalyst unit and manufacturing method thereof - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、触媒が強固に担持された金属ハニカム触媒ユニット及びその製造方法に関するものである。
【０００２】
【従来の技術】
ペーパーコルゲートハニカム担体は、従来よりオゾン分解触媒等の種々の触媒の担体として広く用いられている。ペーパーコルゲートハニカム担体は、その構造上強度が高く触媒担持量を多くでき且つ圧力損失が小さいため好ましい。これらペーパーコルゲートハニカム担体は、通常セラミックペーパー等の無機繊維の不織布を無機バインダー等の接着剤で固定して形成される。
【０００３】
しかし、近年、触媒の用いられる装置の小型化、高性能化等により、より強度が高く圧力損失が小さいペーパーコルゲートハニカム担体が望まれている。このため、セラミックペーパーの代替材料が種々検討されており、アルミ箔等の金属箔や金属板の使用が試みられている。すなわち、アルミ箔等の金属箔は金属箔がセラミックペーパーに比べて強度が高いため、セラミックペーパーよりも厚みを薄くでき、圧力損失を小さくすることができる。
【０００４】
【発明が解決しようとする課題】
しかしながら、金属箔や金属板は、製造段階において圧延する際に油脂等の有機物が付着するため、表面が撥水性を示す。一方、ハニカム担体への触媒の担持方法としては、一般的に、ハニカム担体を金属酸化物等の触媒の水性スラリーに浸漬させた後に乾燥することが行われている。このため、金属箔等の表面が撥水性を示すと、水性スラリーが担体に馴染まずハニカム担体への触媒の担持量が少なくなるため好ましくない。従って、金属箔等を担体として用いる場合には金属箔の表面をアセトン等で脱脂する等により清浄にする必要があるが、このような作業を行うとコストがかさむと共にハニカム担体を接着している有機接着剤が溶け出してハニカム担体の強度も低下するため金属ハニカム担体の実用化の障害の一因になっていた。また、例え金属箔の表面を脱脂して親水性を付与したとしても、金属箔表面とこれに担持される触媒との接着性は十分でなく、触媒が表面から脱落し易いという問題があった。さらに、金属箔等はセラミックペーパー等と異なり繊維間の空隙がなく極めて平滑性に富むため、スラリー浸漬後に乾燥して触媒を金属箔等の表面に担持させても触媒が表面から脱落し易いという問題もあった。
【０００５】
従って、本発明の目的は、表面が疎水性の金属ハニカム担体をそのまま用いて触媒を担持させても、担持した触媒が脱離し難い金属ハニカム触媒ユニット及びその製造方法を提供することにある。
【０００６】
【課題を解決するための手段】
かかる実情において、本発明者は鋭意検討を行った結果、金属ハニカム担体を、親水性樹脂バインダー及び無機バインダーを含む表面処理液と接触させた後に乾燥し、次いで、触媒、前記無機バインダー及び有機バインダーを含む触媒担持スラリーと接触させた後に乾燥すると、疎水性及び親水性のいずれの金属箔等の表面にも親水性樹脂及び無機バインダー固化物からなる親水性表面が形成され、さらに、生成した触媒が該無機バインダー固化物及び有機バインダー固化物により金属ハニカム担体上に強固に担持されることを見出し、本発明を完成するに至った。
【０００７】
すなわち、本発明は、金属ハニカム担体の表面に、親水性樹脂及び無機バインダー固化物を含む表面処理層と、触媒、前記無機バインダー固化物及び有機バインダー固化物を含む触媒担持層とがこの順に形成されており、
該表面処理層に含有される該親水性樹脂が、ポリエステル樹脂、ポリ酢酸ビニル樹脂、ユリアメラミン樹脂であり、該表面処理層中の該親水性樹脂の含有量が、５〜８０重量％であり、
該表面処理層に含有される該無機バインダー固化物が、アルミナゾル、コロイダルシリカ又はチタニアゾルの固化物であり、該表面処理層中の該無機バインダー固化物の含有量が、２０〜９５重量％であり、
該触媒担持層に含有される該触媒の含有量が、８０〜９５重量％であり、
該触媒担持層に含有される該無機バインダー固化物が、アルミナゾル、コロイダルシリカ又はチタニアゾルの固化物であり、該触媒担持層中の該無機バインダー固化物の含有量が、２〜１９．９重量％であり、
該触媒担持層に含有される該有機バインダー固化物が、アクリル系樹脂、ポリエステル系樹脂、ブタジエンラテックス、スチレン系樹脂、酢酸ビニル樹脂、ＳＢＲラテックス又はこれらのエマルジョンの固化物であり、該触媒担持層中の該有機バインダー固化物の含有量が、０．１〜４重量％である
ことを特徴とする金属ハニカム触媒ユニットを提供するものである。
【０００８】
また、本発明は、金属ハニカム担体を、親水性樹脂バインダー及び無機バインダーを含む表面処理液と接触させた後に乾燥し、次いで触媒、前記無機バインダー及び有機バインダーを含む触媒担持スラリーと接触させた後に乾燥する金属ハニカム触媒ユニットの製造方法であり、
該表面処理液に含有される該親水性樹脂バインダーが、ポリエステル樹脂、ポリ酢酸ビニル樹脂、ユリアメラミン樹脂又はこれらのエマルジョンであり、該表面処理液中の該親水性樹脂バインダーの樹脂分の含有量が、０．５〜１０重量％であり、
該表面処理液に含有される該無機バインダーが、アルミナゾル、コロイダルシリカ又はチタニアゾルであり、該表面処理液中の該無機バインダーの固形分の含有量が、１〜２０重量％であり、
該触媒担持スラリーに含有される該触媒の含有量が、５〜５０重量％であり、
該触媒担持スラリーに含有される該無機バインダーが、アルミナゾル、コロイダルシリカ又はチタニアゾルであり、該触媒担持スラリー中の該無機バインダーの固形分の含有量が、１〜１０重量％であり、
該触媒担持スラリーに含有される該有機バインダーが、アクリル系樹脂、ポリエステル系樹脂、ブタジエンラテックス、スチレン系樹脂、酢酸ビニル樹脂、ＳＢＲラテックス又はこれらのエマルジョンであり、該触媒担持スラリー中の該有機バインダーの固形分の含有量が、０．２〜８重量％である
ことを特徴とする金属ハニカム触媒ユニットの製造方法を提供するものである。
【０００９】
【発明の実施の形態】
本発明に係る金属ハニカム触媒ユニットは、金属ハニカム担体を構成する金属板の表面に親水性の表面処理層を形成し、さらに該表面処理層上に触媒担持層を形成したものである。本発明において金属板とは実質的に板状の金属材料全てを含む意味で用い、通常の金属板を含む他、より厚さの薄い金属箔をも含む意味で用いる。金属板の厚さとしては、例えば、通常０．１mm以下、好ましくは１０μm 〜０．０５mmのものが挙げられる。金属板の材質としては、特に限定されず、例えば、アルミニウム、白金、ステンレス、銅等が挙げられるが、このうちアルミニウムであると、軽量で、加工性がよく、硬さ、厚さの種類が豊富で、且つ、安価であるため好ましい。
【００１０】
本発明で用いられる金属ハニカム担体は、平板状金属板と波形状金属板とが交互に積層されてなるものである。このうち、波形状金属板は、平板状金属板をコルゲート加工してなるものであり、金属板の面内の一方向に波が進行するように凹凸が形成されたものである。本発明においてコルゲート加工とは平板状物を波形状物に加工することを意味し、例えば、噛合部分が凹凸形状をなす一組のロール間に平板状物を通す加工方法をいう。
【００１１】
金属ハニカム担体は、上記平板状金属板と波形状金属板とが交互に積層され、この積層が固定されてなるものである。この積層を固定する手段としては、接着剤が用いられる。該接着剤としては、特に限定されないが、例えば、シリカゾル、アルミナゾル、チタニアゾル、セメント等の無機系接着剤；アクリル樹脂系接着剤、酢酸ビニル樹脂系接着剤等の熱可塑性樹脂系接着剤；エポキシ樹脂系接着剤等の熱硬化性樹脂系接着剤が挙げられる。これら接着剤は、上記のものを１種又は２種以上組み合わせて用いることができる。また、接着剤には無機フィラーが配合されていてもよい。接着剤に用いられる無機フィラーとしては、特に限定されない。
【００１２】
本発明に係る金属ハニカム触媒ユニットは、金属ハニカム担体の表面に、表面処理層及び触媒担持層がこの順に形成されてなるものである。本発明において表面処理層とは、金属ハニカム担体の表面を親水性樹脂バインダー及び無機バインダーを含む表面処理液と接触させた後に乾燥して得られる層であり、層中に親水性樹脂及び無機バインダー固化物を含む。本発明において親水性樹脂とは、カルボニル基、アミノ基、スルホン基、カルボキシル基等の親水基を有する樹脂をいい、例えば、ポリエステル樹脂、ポリ酢酸ビニル樹脂、ユリアメラミン樹脂等が挙げられる。また、無機バインダー固化物としては、例えば、アルミナゾル、コロイダルシリカ、チタニアゾル等の無機バインダーが水分の除去等により固化したものが挙げられる。
【００１３】
表面処理層は、通常、層中に親水性樹脂を５〜８０重量％、無機バインダー固化物を２０〜９５重量％含み、好ましくは親水性樹脂を１０〜５０重量％、無機バインダー固化物を５０〜９０重量％含む。親水性樹脂及び無機バインダー固化物の含有量が該範囲内にあると、表面処理層が金属板及び触媒担持層と強固に結合してそれぞれの界面が剥離し難くなり、また、表面処理層が厚くなりすぎないため好ましい。
【００１４】
また、表面処理層中にさらに無機フィラーが含まれると、触媒の担持量を増やす効果があるため好ましい。このような無機フィラーとしては、例えば、アルミナ、シリカ、活性炭等が挙げられる。無機フィラーは、平均粒径が、通常０．０１〜１０μm 、好ましくは０．０１〜５μm である。平均粒径が該範囲内にあると触媒の乗りがよくなって触媒を保持し易くなるため好ましい。
【００１５】
表面処理層に無機フィラーが含まれる場合、通常、層中に親水性樹脂を５〜７０重量％、無機バインダー固化物を１０〜７５重量％及び無機フィラーを２０〜８５重量％含み、好ましくは親水性樹脂を１０〜５０重量％、無機バインダー固化物を２０〜６０重量％及び無機フィラーを３０〜７０重量％含む。なお、表面処理層中には、親水性樹脂、無機バインダー固化物及び無機フィラー以外にも、例えば、触媒、活性炭等が含まれていてもよい。
【００１６】
表面処理層の厚さは、通常５〜１００μm 、好ましくは１０〜５０μm である。層の厚さが該範囲内にあると、触媒スラリーとの接着性を保持しつつ、圧力損失を小さく抑えられるため好ましい。
【００１７】
上記表面処理層は親水基と疎水基の両方を有する親水性樹脂を含むため、油等の有機物が付着している金属板の表面及び清浄な表面の両方に対して親水性樹脂中の疎水基により強固に接着しており、一方触媒の担持の際に接触する触媒担持スラリーに対しても親水性樹脂中の親水基によってよく馴染む。また、上記表面処理層は後述する触媒担持層と同様の無機バインダー固化物を含むため、触媒担持層とも強固に接着する。
【００１８】
本発明に係る金属ハニカム触媒ユニットでは、表面処理層の上に触媒担持層が形成される。本発明において触媒担持層とは、表面処理層が形成された金属ハニカム担体を、触媒、前記無機バインダー及び有機バインダーを含む触媒担持スラリーと接触させた後に乾燥した結果、表面処理層上に形成される層であり、層中に触媒、無機バインダー固化物及び有機バインダー固化物を含む。
【００１９】
本発明で用いられる触媒としては特に限定されないが、例えば、ＭｎＯ2 、活性炭、ＭｎＯ2 とＣｕＯとの複合酸化物等のオゾン分解触媒や、ＭｎＯ2 とＣｕＯとＣｏ2 Ｏ3 との複合酸化物等の脱臭触媒等が挙げられる。また、触媒担持層で用いられる無機バインダー固化物は、表面処理層で用いたものと同一のものが挙げられる。有機バインダー固化物としては、例えば、アクリル系樹脂、ポリエステル系樹脂、ブタジエンラテックス、スチレン系樹脂、酢酸ビニル樹脂、ＳＢＲラテックス等の樹脂又はこれらのエマルジョンからなる有機バインダーが水分の除去等により固化したものが挙げられる。
【００２０】
触媒担持層は、通常、層中に触媒を８０〜９５重量％、無機バインダー固化物を２〜１９．９重量％及び有機バインダー固化物を０．１〜４重量％含み、好ましくは触媒を８０〜９０重量％、無機バインダー固化物を７〜１９．５重量％及び有機バインダー固化物を０．５〜３重量％含む。触媒、無機バインダー固化物及び有機バインダー固化物の含有量が該範囲内にあると、触媒の性能が保持された状態で触媒が強固に担持され触媒の脱落が発生し難くなると共に、触媒担持層が表面処理層と強固に結合して界面が剥離し難くなるため好ましい。また、触媒担持層の厚さは、通常１０〜２００μm 、好ましくは５０〜１５０μm である。層の厚さが該範囲内にあると、触媒の性能が保持された状態で触媒が強固に担持され触媒の脱落が発生し難くなり、圧力損失が高くなりすぎず、且つ、触媒担持層が表面処理層と強固に結合するため好ましい。
【００２１】
本発明に係る金属ハニカム触媒ユニットは、金属ハニカム担体が無機バインダー固化物で被覆されるため耐水性が向上する。また、本発明に係る金属ハニカム触媒ユニットは、表面処理層の無機バインダー固化物と触媒担持層の無機バインダー固化物とで触媒が強固に担持されるため、表面処理層中の親水性樹脂や触媒担持層中の有機バインダー固化物が、触媒や処理ガス等により劣化しても、粉落ちが非常に少ない。
【００２２】
次に本発明に係る金属ハニカム触媒ユニットの製造方法について説明する。該方法は、金属ハニカム担体を、親水性樹脂バインダー及び無機バインダーを含む表面処理液と接触させた後に乾燥し、次いで触媒、前記無機バインダー及び有機バインダーを含む触媒担持スラリーと接触させた後に乾燥するものである。
【００２３】
本発明に係る金属ハニカム触媒ユニットの製造方法では、まず、金属ハニカム担体を親水性樹脂バインダー及び無機バインダーを含む表面処理液と接触させた後に乾燥することにより、金属ハニカム担体を構成する金属板の表面上に表面処理層を形成する。本発明で用いられる表面処理液は、親水性樹脂バインダー及び無機バインダーを含む液状物である。本発明において親水性樹脂バインダーとは、上記本発明に係る金属ハニカム触媒ユニットで用いられる親水性樹脂を含む接着剤であり、具体的には、例えば、カルボニル基、アミノ基、スルホン基、カルボキシル基等の親水基を有する、ポリエステル樹脂、ポリ酢酸ビニル樹脂、ユリアメラミン樹脂等の樹脂接着剤又はこれらのエマルジョン接着剤が挙げられる。また、本発明で用いられる無機バインダーは、上記本発明に係る金属ハニカム触媒ユニットで用いられる無機バインダー固化物の固化前のセラミックスゾルであり、例えば、アルミナゾル、コロイダルシリカ、チタニアゾル等が挙げられる。
【００２４】
表面処理液は、通常、親水性樹脂バインダーの樹脂分を０．５〜１０重量％、無機バインダーの固形分を１〜２０重量％含み、好ましくは親水性樹脂バインダーの樹脂分を２〜７重量％、無機バインダーの固形分を５〜１５重量％含む。親水性樹脂バインダーの樹脂分及び無機バインダーの固形分の含有量が該範囲内にあると、得られる表面処理層が金属板及び触媒担持層と強固に結合してそれぞれの界面が剥離し難くなるため好ましい。
【００２５】
また、表面処理液にさらに無機フィラーが含まれると、１回の含浸で担持できる触媒担持量が多くなるため好ましい。このような無機フィラーとしては、上記本発明に係る金属ハニカム触媒ユニットで用いられる無機フィラーと同様のものが挙げられる。表面処理液にさらに無機フィラーが含まれる場合、表面処理液は、通常、親水性樹脂バインダーの樹脂分を０．５〜１０重量％、無機バインダーの固形分を１〜２０重量％及び無機フィラーを１〜４０重量％含み、好ましくは親水性樹脂バインダーの樹脂分を３〜７重量％、無機バインダーの固形分を５〜１５重量％及び無機フィラーを２０〜３０重量％含む。親水性樹脂バインダーの樹脂分、無機バインダーの固形分及び無機フィラーの含有量が該範囲内にあると、得られる表面処理層が金属板及び触媒担持層と強固に結合してそれぞれの界面が剥離し難くなると共に、金属ハニカム担体中に含浸し易いスラリーとなり、さらに後述の触媒担持スラリーの含浸の回数が例えば１回のように少ない回数でも多量の触媒を担持し易い表面状態を形成するため好ましい。
【００２６】
表面処理液のスラリー濃度は、通常１０〜５０％、好ましくは２５〜４５％である。スラリー濃度が１０％未満であると表面処理層が金属板表面に十分に担持されないため、またスラリー濃度が５０％を越えると増粘して表面処理液の流動性が低下して含浸できなくなるため好ましくない。なお、表面処理液中には、親水性樹脂バインダー、無機バインダー及び無機フィラー以外にも、例えば、消泡剤、分散剤等の助剤が含まれていてもよい。
【００２７】
本発明において表面処理液は親水基と疎水基の両方を有する親水性樹脂バインダーを含むため、油等の有機物が付着している金属板の表面及び清浄な表面の両方に対して親水性樹脂中の疎水基により強固に接着し、乾燥することにより金属板の表面と強固に接着した表面処理層が得られる。また、該表面処理層中に親水基が含まれるため、触媒担持スラリーと接触してもよく馴染む。
【００２８】
金属ハニカム担体を表面処理液と接触させた後に乾燥する場合、その乾燥温度は、通常６０〜２００℃、好ましくは１００〜１４０℃である。乾燥温度が２００℃を越えると、親水性樹脂が劣化するおそれがあるため好ましくない。該乾燥により、金属ハニカム担体の表面に表面処理層が形成される。
【００２９】
次いで、触媒、前記無機バインダー及び有機バインダーを含む触媒担持スラリーと接触させた後に乾燥することにより、表面処理層上に触媒担持層を形成する。本発明で用いられる触媒担持スラリーは、触媒、前記無機バインダー及び有機バインダーを含むスラリーである。本発明で用いられる触媒としては、２００℃以上の加熱処理を必要としないものが挙げられ、上記本発明に係る金属ハニカム触媒ユニットで用いられる触媒と同様のものが挙げられる。無機バインダーとしては、上記表面処理液で用いられる無機バインダーと同様のものが挙げられる。無機バインダーは、特に、表面処理液で用いたものと同一のものを用いると、表面処理層と触媒担持層との間で層間の結合が強固になるため好ましい。
【００３０】
本発明で用いられる有機バインダーは、上記本発明に係る金属ハニカム触媒ユニットで用いられる有機バインダー固化物の固化前の樹脂又はそのエマルジョンであり、例えば、アクリル系樹脂、ポリエステル系樹脂、ブタジエンラテックス、スチレン系樹脂、酢酸ビニル樹脂、ＳＢＲラテックス等の樹脂又はこれらのエマルジョンが挙げられる。このように触媒担持スラリーに有機バインダーを配合することにより、触媒担持スラリーと表面処理層中の親水性樹脂との馴染みがよくなり層間で剥離し難くなると共に、触媒が強固に担持され脱落し難くなるため好ましい。
【００３１】
触媒担持スラリーは、通常、触媒を５〜５０重量％、無機バインダーの固形分を１〜１０重量％及び有機バインダーの固形分を０．２〜８重量％含み、好ましくは触媒を１０〜４０重量％、無機バインダーの固形分を２〜８重量％及び有機バインダーの固形分を０．５〜３重量％含む。触媒、無機バインダーの固形分及び有機バインダーの固形分の含有量が該範囲内にあると、触媒性能を保持したまま粉落ちを防ぐことができる。
【００３２】
また、触媒担持スラリーのスラリー濃度は、通常１０〜６０％、好ましくは２０〜４０％である。スラリー濃度が１０％未満であると触媒担持層が十分に形成されないため、またスラリー濃度が６０％を越えると増粘し触媒担持スラリーの流動性が低下してセルが目詰まりを起こし易いため好ましくない。
【００３３】
本発明において触媒担持スラリーは触媒と共に前記表面処理層の形成に用いたのと同様の無機バインダー及び有機バインダーを用いるため、同様の無機バインダーの固化物及び親水性樹脂を含む表面処理層と強固に接着した触媒担持層が得られ、金属ハニカム担体との界面で剥離し難く、触媒が強固に担持され脱落し難い。
【００３４】
表面処理された金属ハニカム担体を触媒担持スラリーと接触させた後に乾燥する場合、その乾燥温度は、通常６０〜２００℃、好ましくは１００〜１４０℃である。乾燥温度が２００℃を越えると、親水性樹脂が劣化するおそれがあるため好ましくない。該乾燥により、表面処理層の表面に触媒担持層が形成される。
【００３５】
本発明に係る金属ハニカム担体触媒ユニットは、コピー機等に用いられるオゾンフィルター、冷蔵庫やトイレ脱臭機などに用いられる脱臭フィルター等に使用できる。
【００３６】
【実施例】
次に、実施例を挙げて本発明をさらに具体的に説明するが、本発明はこれに限定されるものではない。
【００３７】
実施例１
厚さ０．０３mmのアルミ箔をコルゲート加工するものと、コルゲート加工しないものとに分け、コルゲート加工するものを、上下一対の波形段ロールの間に通してコルゲート状アルミ箔とした。
得られたコルゲート状アルミ箔の山部にポリエステル系熱可塑性樹脂のエマルジョン（商品名アロンメルト、東亜合成株式会社製、樹脂分３０重量％）を塗布した後、該コルゲート状アルミ箔をコルゲート加工しない平板状アルミ箔と共に１９０℃に加熱した段ロールに通した。このコルゲート状アルミ箔は、段ロールを通過する０．２秒の間に段ロールの山部においてエマルジョンの水分が蒸発すると共にポリエステル樹脂が溶融し、この状態でコルゲート加工していない平坦状アルミ箔と共に０．５MPa で加圧し、段ロールの通過後に自然冷却することにより接着して、コルゲート状アルミ箔と平坦状アルミ箔とがコルゲート状アルミ箔の山部で接着され一体化されたアルミ箔（アルミハニカム基本構造体）を得た。
このアルミハニカム基本構造体を長さ１７０mmに切断し、コルゲート状アルミ箔の山部にアクリル樹脂系接着剤を塗布して複数積層し、乾燥して、１７０mm×１７０mm×２１０mmのアルミハニカム構造体を得た。得られたアルミハニカム構造体は、波形コルゲートのピッチが２．０mm、セル高さが０．８mmであった。次に、このアルミハニカム構造体を厚さ１０mmに切断して、十分な強度を有する１７０mm×１７０mm×１０mmの平板状のアルミハニカム構造体を得た。
得られた平板状のアルミハニカム構造体を上記と同様のポリエステル系熱可塑性樹脂のエマルジョンを１０重量部（樹脂分として３重量部）、固形分３０重量％のコロイダルシリカを２０重量部（固形分として６重量部）、水９０重量部からなる表面処理液に浸漬し、引き揚げた後１１０℃で１時間乾燥した。
乾燥後の平板状のアルミハニカム構造体を、オゾン分解触媒としてＭｎＯ2 １８重量部、固形分３０重量％のコロイダルシリカを１４重量部（固形分として４．２重量部）、アクリル樹脂系エマルジョン（商品名アクロナール、ＢＡＳＦディスパージョン株式会社製、樹脂分３０重量％）４重量部（樹脂分として１．２重量部）及び水６４重量部からなる触媒担持スラリーに浸漬し、引き揚げた後１４０℃で１時間乾燥した。
得られたオゾン分解フィルターは、ポリエステル系熱可塑性樹脂の固化物を３０重量％、コロイダルシリカの固化物を７０重量％含む表面処理層が厚さ３０μm に形成されると共に、ＭｎＯ2 を８０重量％、コロイダルシリカの固化物を１８重量％、アクリル樹脂を２重量％含む触媒担持層が厚さ１５０μm に形成されていた。
また、得られたオゾン分解フィルターについて粉落ち具合を調べたところ、粉落ち量はオゾン分解フィルター１L 当たり０．０２g 以下であり、非常に少なかった。粉落ち具合は以下のようにして調べた。
（粉落ち具合の測定方法）
オゾン分解フィルターを、高さ１００mmからプラスチック板に１０回落下させたときの、オゾン分解フィルターから脱落した粉の重量の合計量を測定した。これを３つの試料について測定し、平均値を求めた。
【００３８】
比較例１
平板状のアルミハニカム構造体を、表面処理液に浸漬、乾燥しなかった以外は、実施例１と同様にしてオゾン分解フィルターの作製を試みた。
しかし、平板状のアルミハニカム構造体の表面が、触媒担持スラリーをはじいたため、触媒を担持することができなかった。
【００３９】
比較例２
実施例１の触媒担持スラリーに代えて、オゾン分解触媒としてＭｎＯ2 １８重量部及び水８２重量部からなる触媒担持スラリーを用いた以外は、実施例１と同様にしてオゾン分解フィルターを作製した。
得られたオゾン分解フィルターについて、実施例１と同様に粉落ち具合を調べたところ、粉落ち量はオゾン分解フィルター１L 当たり５．０g 以上であり、多かった。
【００４０】
【発明の効果】
本発明に係る金属ハニカム触媒ユニットによれば、触媒が金属ハニカム担体に強固に結合したものとなる。また、本発明に係る金属ハニカム触媒ユニットの製造方法によれば、表面が疎水性の金属ハニカム担体をそのまま用い、特段の表面処理をすることなく触媒を担持させても、担持した触媒が脱離し難い金属ハニカム触媒ユニットが得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a metal honeycomb catalyst unit in which a catalyst is firmly supported and a method for manufacturing the same.
[0002]
[Prior art]
A paper corrugated honeycomb carrier has been widely used as a carrier for various catalysts such as an ozone decomposition catalyst. A paper corrugated honeycomb carrier is preferable because of its high strength and high catalyst loading, and low pressure loss. These paper corrugated honeycomb carriers are usually formed by fixing a non-woven fabric of inorganic fibers such as ceramic paper with an adhesive such as an inorganic binder.
[0003]
However, in recent years, a paper corrugated honeycomb carrier having higher strength and lower pressure loss is desired due to downsizing and higher performance of an apparatus using a catalyst. For this reason, various alternative materials for ceramic paper have been studied, and attempts have been made to use metal foils such as aluminum foil and metal plates. That is, since metal foil, such as aluminum foil, has higher strength than ceramic paper, it can be made thinner than ceramic paper and pressure loss can be reduced.
[0004]
[Problems to be solved by the invention]
However, the surface of the metal foil or metal plate exhibits water repellency because organic substances such as fats and oils adhere to the metal foil or metal plate when rolled in the production stage. On the other hand, as a method for supporting a catalyst on a honeycomb carrier, generally, the honeycomb carrier is immersed in an aqueous slurry of a catalyst such as a metal oxide and then dried. For this reason, it is not preferable that the surface of the metal foil or the like exhibits water repellency because the aqueous slurry does not conform to the carrier and the amount of catalyst supported on the honeycomb carrier decreases. Therefore, when a metal foil or the like is used as a carrier, it is necessary to clean the surface of the metal foil by degreasing with acetone or the like. However, such an operation increases the cost and bonds the honeycomb carrier. Since the organic adhesive melts and the strength of the honeycomb carrier also decreases, it has been one of the obstacles to the practical use of the metal honeycomb carrier. Moreover, even if the surface of the metal foil is degreased to impart hydrophilicity, there is a problem that the adhesion between the metal foil surface and the catalyst supported by the metal foil surface is not sufficient, and the catalyst easily falls off the surface. . Furthermore, unlike ceramic paper, metal foil, etc. has no gaps between fibers and is extremely smooth. Therefore, even if the catalyst is supported on the surface of the metal foil, etc. by drying after slurry immersion, the catalyst can easily fall off the surface. There was also a problem.
[0005]
Accordingly, an object of the present invention is to provide a metal honeycomb catalyst unit in which the supported catalyst is difficult to be detached even when the catalyst is supported using the metal honeycomb carrier having a hydrophobic surface as it is, and a method for manufacturing the same.
[0006]
[Means for Solving the Problems]
In such a situation, the present inventor has intensively studied, and as a result, the metal honeycomb carrier is dried after contacting with the surface treatment liquid containing the hydrophilic resin binder and the inorganic binder, and then the catalyst, the inorganic binder and the organic binder are dried. When dried after contacting with the catalyst-carrying slurry containing, a hydrophilic surface made of a hydrophilic resin and a solidified inorganic binder is formed on the surface of both hydrophobic and hydrophilic metal foils, and the produced catalyst Has been found to be firmly supported on the metal honeycomb carrier by the solidified inorganic binder and solidified organic binder, and the present invention has been completed.
[0007]
That is, according to the present invention, a surface treatment layer containing a hydrophilic resin and an inorganic binder solidified product and a catalyst, a catalyst supporting layer containing the inorganic binder solidified product and an organic binder solidified product are formed in this order on the surface of the metal honeycomb carrier. Has been
The hydrophilic resin contained in the surface treatment layer is a polyester resin, a polyvinyl acetate resin, or a urea melamine resin, and the content of the hydrophilic resin in the surface treatment layer is 5 to 80% by weight. ,
The inorganic binder solidified product contained in the surface treatment layer is a solidified product of alumina sol, colloidal silica or titania sol, and the content of the inorganic binder solidified product in the surface treatment layer is 20 to 95% by weight. ,
The content of the catalyst contained in the catalyst support layer is 80 to 95% by weight,
The inorganic binder solidified product contained in the catalyst support layer is a solidified product of alumina sol, colloidal silica or titania sol, and the content of the inorganic binder solidified product in the catalyst support layer is 2 to 19.9% by weight. And
The organic binder solidified product contained in the catalyst support layer is an acrylic resin, polyester resin, butadiene latex, styrene resin, vinyl acetate resin, SBR latex or a solidified product of these emulsions, and the catalyst support layer The content of the organic binder solidified product is 0.1 to 4% by weight. A metal honeycomb catalyst unit is provided.
[0008]
In the present invention, the metal honeycomb carrier is contacted with a surface treatment liquid containing a hydrophilic resin binder and an inorganic binder, dried, and then contacted with a catalyst, a catalyst-carrying slurry containing the inorganic binder and the organic binder. A method for producing a metal honeycomb catalyst unit to be dried ,
The hydrophilic resin binder contained in the surface treatment liquid is a polyester resin, a polyvinyl acetate resin, a urea melamine resin, or an emulsion thereof, and the resin content of the hydrophilic resin binder in the surface treatment liquid Is 0.5 to 10% by weight,
The inorganic binder contained in the surface treatment liquid is alumina sol, colloidal silica or titania sol, and the solid content of the inorganic binder in the surface treatment liquid is 1 to 20% by weight,
The content of the catalyst contained in the catalyst-carrying slurry is 5 to 50% by weight,
The inorganic binder contained in the catalyst-carrying slurry is alumina sol, colloidal silica or titania sol, and the solid content of the inorganic binder in the catalyst-carrying slurry is 1 to 10% by weight,
The organic binder contained in the catalyst-carrying slurry is an acrylic resin, a polyester resin, a butadiene latex, a styrene resin, a vinyl acetate resin, an SBR latex, or an emulsion thereof, and the organic binder in the catalyst-carrying slurry The present invention provides a method for manufacturing a metal honeycomb catalyst unit, characterized in that the solid content is 0.2 to 8% by weight .
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The metal honeycomb catalyst unit according to the present invention is obtained by forming a hydrophilic surface treatment layer on the surface of a metal plate constituting a metal honeycomb carrier, and further forming a catalyst support layer on the surface treatment layer. In the present invention, the term “metal plate” is used to include substantially all plate-shaped metal materials, and includes a normal metal plate and also includes a metal foil having a smaller thickness. The thickness of the metal plate is, for example, usually 0.1 mm or less, preferably 10 μm to 0.05 mm. The material of the metal plate is not particularly limited, and examples thereof include aluminum, platinum, stainless steel, copper, and the like. Of these, aluminum is lightweight, has good workability, and has various types of hardness and thickness. It is preferable because it is abundant and inexpensive.
[0010]
The metal honeycomb carrier used in the present invention is obtained by alternately laminating flat metal plates and corrugated metal plates. Of these, the corrugated metal plate is obtained by corrugating a flat metal plate, and is formed with irregularities so that the wave travels in one direction within the surface of the metal plate. In the present invention, corrugating means that a flat plate is processed into a corrugated material. For example, the corrugated processing refers to a processing method in which a flat plate is passed between a pair of rolls having meshed portions.
[0011]
The metal honeycomb carrier is obtained by alternately laminating the flat metal plate and the corrugated metal plate, and fixing the laminate. An adhesive is used as a means for fixing this lamination. Examples of the adhesive include, but are not limited to, inorganic adhesives such as silica sol, alumina sol, titania sol, and cement; thermoplastic resin adhesives such as acrylic resin adhesives and vinyl acetate resin adhesives; epoxy resins And thermosetting resin adhesives such as adhesives. These adhesives can be used alone or in combination of two or more thereof. In addition, an inorganic filler may be blended in the adhesive. It does not specifically limit as an inorganic filler used for an adhesive agent.
[0012]
The metal honeycomb catalyst unit according to the present invention has a surface treatment layer and a catalyst support layer formed in this order on the surface of a metal honeycomb carrier. In the present invention, the surface treatment layer is a layer obtained by bringing the surface of the metal honeycomb carrier into contact with a surface treatment liquid containing a hydrophilic resin binder and an inorganic binder and then drying, and the hydrophilic resin and the inorganic binder are contained in the layer. Includes solidified material. In the present invention, the hydrophilic resin refers to a resin having a hydrophilic group such as a carbonyl group, an amino group, a sulfone group, or a carboxyl group, and examples thereof include a polyester resin, a polyvinyl acetate resin, and a urea melamine resin. Examples of the solidified inorganic binder include those obtained by solidifying an inorganic binder such as alumina sol, colloidal silica, and titania sol by removing moisture.
[0013]
The surface treatment layer usually contains 5 to 80% by weight of the hydrophilic resin and 20 to 95% by weight of the inorganic binder solidified material, preferably 10 to 50% by weight of the hydrophilic resin and 50 inorganic binder solidified material. Contains ~ 90% by weight. When the content of the hydrophilic resin and the solidified inorganic binder is within this range, the surface treatment layer is firmly bonded to the metal plate and the catalyst supporting layer, and the respective interfaces are difficult to peel off. It is preferable because it does not become too thick.
[0014]
Further, when an inorganic filler is further contained in the surface treatment layer, it is preferable because it has an effect of increasing the amount of the catalyst supported. Examples of such inorganic fillers include alumina, silica, activated carbon and the like. The inorganic filler has an average particle size of usually 0.01 to 10 μm, preferably 0.01 to 5 μm. It is preferable that the average particle diameter is within this range because the catalyst can be easily loaded and the catalyst can be easily retained.
[0015]
When the surface treatment layer contains an inorganic filler, it usually contains 5 to 70% by weight of a hydrophilic resin, 10 to 75% by weight of an inorganic binder solidified product, and 20 to 85% by weight of an inorganic filler, preferably hydrophilic. 10 to 50% by weight of a functional resin, 20 to 60% by weight of an inorganic binder solidified product, and 30 to 70% by weight of an inorganic filler. The surface treatment layer may contain, for example, a catalyst, activated carbon, etc. in addition to the hydrophilic resin, the inorganic binder solidified product, and the inorganic filler.
[0016]
The thickness of the surface treatment layer is usually 5 to 100 μm, preferably 10 to 50 μm. It is preferable for the thickness of the layer to fall within this range because pressure loss can be kept small while maintaining adhesion to the catalyst slurry.
[0017]
Since the surface treatment layer includes a hydrophilic resin having both a hydrophilic group and a hydrophobic group, the hydrophobic group in the hydrophilic resin with respect to both the surface of the metal plate to which an organic substance such as oil adheres and the clean surface. On the other hand, it adheres well to the catalyst-carrying slurry that comes into contact with the catalyst when supported by the hydrophilic group in the hydrophilic resin. Moreover, since the said surface treatment layer contains the same inorganic binder solidified material as the catalyst support layer mentioned later, it adheres firmly also with a catalyst support layer.
[0018]
In the metal honeycomb catalyst unit according to the present invention, a catalyst support layer is formed on the surface treatment layer. In the present invention, the catalyst support layer is formed on the surface treatment layer as a result of drying after the metal honeycomb carrier on which the surface treatment layer is formed is brought into contact with the catalyst support slurry containing the catalyst, the inorganic binder and the organic binder. The layer includes a catalyst, a solidified inorganic binder and a solidified organic binder.
[0019]
The catalyst used in the present invention is not particularly limited. For example, an ozone decomposition catalyst such as MnO 2 , activated carbon, a composite oxide of MnO 2 and CuO, or a composite oxide of MnO 2 , CuO and Co 2 O 3 is used. And the like. The inorganic binder solidified product used in the catalyst support layer may be the same as that used in the surface treatment layer. As the organic binder solidified product, for example, a resin such as an acrylic resin, a polyester resin, a butadiene latex, a styrene resin, a vinyl acetate resin, an SBR latex, or an organic binder made of these emulsions is solidified by removing water. Is mentioned.
[0020]
The catalyst-supporting layer usually contains 80 to 95% by weight of catalyst, 2 to 19.9% by weight of inorganic binder solidified product, and 0.1 to 4% by weight of organic binder solidified product, and preferably 80% of catalyst. -90 wt%, inorganic binder solidified product 7-19.5 wt% and organic binder solidified product 0.5 to 3 wt%. When the content of the catalyst, the inorganic binder solidified product and the organic binder solidified product is within this range, the catalyst is firmly supported in a state where the performance of the catalyst is maintained, and it is difficult for the catalyst to fall off. Is preferable because it is firmly bonded to the surface treatment layer and the interface is hardly peeled off. The thickness of the catalyst support layer is usually 10 to 200 μm, preferably 50 to 150 μm. If the thickness of the layer is within this range, the catalyst is firmly supported while the performance of the catalyst is maintained, the catalyst is less likely to fall off, the pressure loss is not excessively high, and the catalyst supporting layer is This is preferable because it is firmly bonded to the surface treatment layer.
[0021]
The metal honeycomb catalyst unit according to the present invention is improved in water resistance because the metal honeycomb carrier is coated with the solidified inorganic binder. Further, in the metal honeycomb catalyst unit according to the present invention, since the catalyst is firmly supported by the inorganic binder solidified product of the surface treatment layer and the inorganic binder solidified product of the catalyst support layer, the hydrophilic resin or catalyst in the surface treatment layer is used. Even if the organic binder solidified material in the support layer is deteriorated by a catalyst, a processing gas, or the like, powder falling is very small.
[0022]
Next, a method for manufacturing the metal honeycomb catalyst unit according to the present invention will be described. In this method, the metal honeycomb carrier is dried after being brought into contact with a surface treatment liquid containing a hydrophilic resin binder and an inorganic binder, and then dried after being brought into contact with a catalyst, a catalyst-carrying slurry containing the inorganic binder and the organic binder. Is.
[0023]
In the method for manufacturing a metal honeycomb catalyst unit according to the present invention, first, the metal honeycomb carrier is brought into contact with a surface treatment liquid containing a hydrophilic resin binder and an inorganic binder and then dried, whereby a metal plate constituting the metal honeycomb carrier is formed. A surface treatment layer is formed on the surface. The surface treatment liquid used in the present invention is a liquid material containing a hydrophilic resin binder and an inorganic binder. In the present invention, the hydrophilic resin binder is an adhesive containing a hydrophilic resin used in the metal honeycomb catalyst unit according to the present invention, and specifically includes, for example, a carbonyl group, an amino group, a sulfone group, and a carboxyl group. Examples thereof include resin adhesives such as polyester resins, polyvinyl acetate resins, urea melamine resins, and emulsion adhesives having hydrophilic groups such as these. The inorganic binder used in the present invention is a ceramic sol before solidifying the inorganic binder solidified product used in the metal honeycomb catalyst unit according to the present invention, and examples thereof include alumina sol, colloidal silica, and titania sol.
[0024]
The surface treatment liquid usually contains 0.5 to 10% by weight of the resin content of the hydrophilic resin binder and 1 to 20% by weight of the solid content of the inorganic binder, preferably 2 to 7% by weight of the resin content of the hydrophilic resin binder. %, 5-15% by weight of the solid content of the inorganic binder. When the resin content of the hydrophilic resin binder and the solid content of the inorganic binder are within the above ranges, the obtained surface treatment layer is firmly bonded to the metal plate and the catalyst supporting layer, and the respective interfaces are difficult to peel off. Therefore, it is preferable.
[0025]
Further, it is preferable that an inorganic filler is further contained in the surface treatment liquid because the amount of catalyst supported that can be supported by one impregnation increases. As such an inorganic filler, the thing similar to the inorganic filler used with the said metal honeycomb catalyst unit which concerns on this invention is mentioned. When the surface treatment liquid further contains an inorganic filler, the surface treatment liquid usually contains 0.5 to 10% by weight of the resin content of the hydrophilic resin binder, 1 to 20% by weight of the solid content of the inorganic binder, and the inorganic filler. 1 to 40% by weight, preferably 3 to 7% by weight of the resin content of the hydrophilic resin binder, 5 to 15% by weight of the solid content of the inorganic binder, and 20 to 30% by weight of the inorganic filler. When the resin content of the hydrophilic resin binder, the solid content of the inorganic binder, and the content of the inorganic filler are within the above ranges, the resulting surface treatment layer is firmly bonded to the metal plate and the catalyst support layer, and the respective interfaces peel off. This is preferable because it becomes a slurry that is easily impregnated in the metal honeycomb carrier and forms a surface state in which a large amount of catalyst is easily supported even when the number of impregnations of the catalyst support slurry described below is small, for example, once. .
[0026]
The slurry concentration of the surface treatment liquid is usually 10 to 50%, preferably 25 to 45%. If the slurry concentration is less than 10%, the surface treatment layer is not sufficiently supported on the surface of the metal plate, and if the slurry concentration exceeds 50%, the viscosity of the surface treatment liquid is increased and the fluidity of the surface treatment solution is lowered, making impregnation impossible. It is not preferable. In addition to the hydrophilic resin binder, the inorganic binder, and the inorganic filler, the surface treatment liquid may contain auxiliary agents such as an antifoaming agent and a dispersing agent.
[0027]
In the present invention, since the surface treatment liquid contains a hydrophilic resin binder having both a hydrophilic group and a hydrophobic group, the surface treatment liquid is contained in the hydrophilic resin with respect to both the surface of the metal plate to which an organic substance such as oil is adhered and the clean surface. The surface treatment layer strongly bonded to the surface of the metal plate can be obtained by firmly bonding with the hydrophobic group and drying. Further, since the surface treatment layer contains a hydrophilic group, it may be brought into contact with the catalyst-carrying slurry.
[0028]
When the metal honeycomb carrier is dried after being brought into contact with the surface treatment liquid, the drying temperature is usually 60 to 200 ° C, preferably 100 to 140 ° C. If the drying temperature exceeds 200 ° C., the hydrophilic resin may be deteriorated, which is not preferable. By the drying, a surface treatment layer is formed on the surface of the metal honeycomb carrier.
[0029]
Subsequently, after making it contact with the catalyst carrying slurry containing a catalyst, the said inorganic binder, and an organic binder, it dries, and forms a catalyst carrying layer on a surface treatment layer. The catalyst-carrying slurry used in the present invention is a slurry containing a catalyst, the inorganic binder, and an organic binder. Examples of the catalyst used in the present invention include those that do not require heat treatment at 200 ° C. or higher, and examples include the same catalysts as those used in the metal honeycomb catalyst unit according to the present invention. Examples of the inorganic binder include those similar to the inorganic binder used in the surface treatment liquid. In particular, it is preferable to use the same inorganic binder as that used in the surface treatment liquid because the bonding between the surface treatment layer and the catalyst supporting layer becomes strong.
[0030]
The organic binder used in the present invention is a resin or an emulsion before solidification of the organic binder solidified product used in the metal honeycomb catalyst unit according to the present invention. For example, acrylic resin, polyester resin, butadiene latex, styrene Resin such as resin, vinyl acetate resin, SBR latex, or emulsion thereof. By blending the organic binder with the catalyst-carrying slurry in this manner, the familiarity between the catalyst-carrying slurry and the hydrophilic resin in the surface treatment layer is improved, and it is difficult to peel off between the layers, and the catalyst is firmly supported and difficult to fall off. Therefore, it is preferable.
[0031]
The catalyst-supporting slurry usually contains 5 to 50% by weight of the catalyst, 1 to 10% by weight of the solid content of the inorganic binder, and 0.2 to 8% by weight of the solid content of the organic binder, preferably 10 to 40% by weight of the catalyst. %, 2-8% by weight of the solid content of the inorganic binder and 0.5-3% by weight of the solid content of the organic binder. When the content of the solid content of the catalyst, the inorganic binder, and the solid content of the organic binder is within this range, powder falling can be prevented while maintaining the catalyst performance.
[0032]
The slurry concentration of the catalyst-carrying slurry is usually 10 to 60%, preferably 20 to 40%. If the slurry concentration is less than 10%, the catalyst-carrying layer is not sufficiently formed, and if the slurry concentration exceeds 60%, the viscosity of the catalyst-carrying slurry is increased and the fluidity of the catalyst-carrying slurry is lowered and the cell is likely to be clogged. Absent.
[0033]
In the present invention, the catalyst-carrying slurry uses the same inorganic binder and organic binder as those used for the formation of the surface treatment layer together with the catalyst. Therefore, the catalyst-carrying slurry is solid with the surface treatment layer containing the same solidified inorganic binder and hydrophilic resin. An adhered catalyst support layer is obtained, and is difficult to peel off at the interface with the metal honeycomb carrier, and the catalyst is firmly supported and is not easily removed.
[0034]
When the surface-treated metal honeycomb carrier is dried after being brought into contact with the catalyst-carrying slurry, the drying temperature is usually 60 to 200 ° C, preferably 100 to 140 ° C. If the drying temperature exceeds 200 ° C., the hydrophilic resin may be deteriorated, which is not preferable. By the drying, a catalyst supporting layer is formed on the surface of the surface treatment layer.
[0035]
The metal honeycomb carrier catalyst unit according to the present invention can be used for an ozone filter used in a copy machine or the like, a deodorization filter used in a refrigerator, a toilet deodorizer, or the like.
[0036]
【Example】
Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
[0037]
Example 1
The corrugated aluminum foil having a thickness of 0.03 mm was divided into a corrugated aluminum foil and a corrugated aluminum foil that was not corrugated and passed between a pair of upper and lower corrugated rolls.
A flat plate on which the corrugated aluminum foil is not corrugated after the emulsion of the polyester-based thermoplastic resin (trade name: Aronmelt, manufactured by Toa Gosei Co., Ltd., resin content: 30% by weight) is applied to the peak of the corrugated aluminum foil. It passed through the corrugated roll heated at 190 degreeC with the shape aluminum foil. This corrugated aluminum foil is a flat aluminum foil that has not been corrugated in this state as the water content of the emulsion evaporates and the polyester resin melts at the peak of the corrugated roll in 0.2 seconds passing through the corrugated roll. Together with pressurizing at 0.5 MPa and naturally cooling after passing through the corrugated roll, and the corrugated aluminum foil and the flat aluminum foil are bonded and integrated at the peak of the corrugated aluminum foil ( An aluminum honeycomb basic structure) was obtained.
This aluminum honeycomb basic structure is cut to a length of 170 mm, a plurality of layers of an acrylic resin adhesive is applied to the crests of corrugated aluminum foil, and a plurality of layers are laminated and dried to form an aluminum honeycomb structure of 170 mm × 170 mm × 210 mm. Obtained. The obtained aluminum honeycomb structure had a corrugated corrugated pitch of 2.0 mm and a cell height of 0.8 mm. Next, this aluminum honeycomb structure was cut into a thickness of 10 mm to obtain a flat aluminum honeycomb structure of 170 mm × 170 mm × 10 mm having sufficient strength.
The obtained plate-like aluminum honeycomb structure was obtained by adding 10 parts by weight of the same polyester-based thermoplastic resin emulsion (3 parts by weight as the resin) and 20 parts by weight of the colloidal silica having a solid content of 30% by weight (solid content). As 6 parts by weight), dipped in a surface treatment solution consisting of 90 parts by weight of water, lifted, and dried at 110 ° C. for 1 hour.
The dried plate-like aluminum honeycomb structure was prepared by using 18 parts by weight of MnO 2 as an ozone decomposition catalyst, 14 parts by weight of colloidal silica having a solid content of 30% by weight (4.2 parts by weight as a solid content), an acrylic resin emulsion ( Product name Acronal, manufactured by BASF Dispersion Co., Ltd., 30% by weight of resin) 4 parts by weight (1.2 parts by weight as resin content) and 64 parts by weight of water were immersed in a catalyst-carrying slurry and pulled up at 140 ° C. Dried for 1 hour.
The obtained ozonolysis filter has a surface treatment layer containing 30% by weight of a solidified polyester-based thermoplastic resin and 70% by weight of a solidified colloidal silica having a thickness of 30 μm and 80% by weight of MnO 2. Further, a catalyst supporting layer containing 18% by weight of solidified colloidal silica and 2% by weight of acrylic resin was formed to a thickness of 150 μm.
Moreover, when the degree of powder removal was investigated about the obtained ozone decomposition filter, the amount of powder removal was 0.02 g or less per liter of the ozone decomposition filter, which was very small. The degree of powder removal was examined as follows.
(Measurement method of powder removal)
When the ozonolysis filter was dropped 10 times from a height of 100 mm onto a plastic plate, the total amount of the powder dropped from the ozonolysis filter was measured. This was measured for three samples, and the average value was determined.
[0038]
Comparative Example 1
An ozonolysis filter was produced in the same manner as in Example 1 except that the flat aluminum honeycomb structure was not immersed and dried in the surface treatment liquid.
However, since the surface of the flat aluminum honeycomb structure repelled the catalyst-carrying slurry, the catalyst could not be carried.
[0039]
Comparative Example 2
An ozone decomposition filter was produced in the same manner as in Example 1 except that instead of the catalyst support slurry of Example 1, a catalyst support slurry consisting of 18 parts by weight of MnO 2 and 82 parts by weight of water was used as the ozone decomposition catalyst.
About the obtained ozone decomposition filter, when the powder fall condition was investigated similarly to Example 1, the amount of powder fall was 5.0g or more per 1L of ozone decomposition filters, and there were many.
[0040]
【The invention's effect】
According to the metal honeycomb catalyst unit of the present invention, the catalyst is firmly bonded to the metal honeycomb carrier. Further, according to the method for manufacturing a metal honeycomb catalyst unit according to the present invention, the supported catalyst is detached even if the metal honeycomb carrier having a hydrophobic surface is used as it is and the catalyst is supported without any special surface treatment. A difficult metal honeycomb catalyst unit is obtained.
Claims (6)
該表面処理層に含有される該親水性樹脂が、ポリエステル樹脂、ポリ酢酸ビニル樹脂、ユリアメラミン樹脂であり、該表面処理層中の該親水性樹脂の含有量が、５〜８０重量％であり、
該表面処理層に含有される該無機バインダー固化物が、アルミナゾル、コロイダルシリカ又はチタニアゾルの固化物であり、該表面処理層中の該無機バインダー固化物の含有量が、２０〜９５重量％であり、
該触媒担持層に含有される該触媒の含有量が、８０〜９５重量％であり、
該触媒担持層に含有される該無機バインダー固化物が、アルミナゾル、コロイダルシリカ又はチタニアゾルの固化物であり、該触媒担持層中の該無機バインダー固化物の含有量が、２〜１９．９重量％であり、
該触媒担持層に含有される該有機バインダー固化物が、アクリル系樹脂、ポリエステル系樹脂、ブタジエンラテックス、スチレン系樹脂、酢酸ビニル樹脂、ＳＢＲラテックス又はこれらのエマルジョンの固化物であり、該触媒担持層中の該有機バインダー固化物の含有量が、０．１〜４重量％である
ことを特徴とする金属ハニカム触媒ユニット。On the surface of the metal honeycomb carrier, a surface treatment layer containing a hydrophilic resin and an inorganic binder solidified product, and a catalyst, a catalyst supporting layer containing the inorganic binder solidified product and an organic binder solidified product, are formed in this order .
The hydrophilic resin contained in the surface treatment layer is a polyester resin, a polyvinyl acetate resin, or a urea melamine resin, and the content of the hydrophilic resin in the surface treatment layer is 5 to 80% by weight. ,
The inorganic binder solidified product contained in the surface treatment layer is a solidified product of alumina sol, colloidal silica or titania sol, and the content of the inorganic binder solidified product in the surface treatment layer is 20 to 95% by weight. ,
The content of the catalyst contained in the catalyst support layer is 80 to 95% by weight,
The inorganic binder solidified product contained in the catalyst support layer is a solidified product of alumina sol, colloidal silica or titania sol, and the content of the inorganic binder solidified product in the catalyst support layer is 2 to 19.9% by weight. And
The organic binder solidified product contained in the catalyst support layer is an acrylic resin, polyester resin, butadiene latex, styrene resin, vinyl acetate resin, SBR latex or a solidified product of these emulsions, and the catalyst support layer The metal honeycomb catalyst unit , wherein the content of the solidified organic binder is 0.1 to 4% by weight .
該表面処理液に含有される該親水性樹脂バインダーが、ポリエステル樹脂、ポリ酢酸ビニル樹脂、ユリアメラミン樹脂又はこれらのエマルジョンであり、該表面処理液中の該親水性樹脂バインダーの樹脂分の含有量が、０．５〜１０重量％であり、
該表面処理液に含有される該無機バインダーが、アルミナゾル、コロイダルシリカ又はチタニアゾルであり、該表面処理液中の該無機バインダーの固形分の含有量が、１〜２０重量％であり、
該触媒担持スラリーに含有される該触媒の含有量が、５〜５０重量％であり、
該触媒担持スラリーに含有される該無機バインダーが、アルミナゾル、コロイダルシリカ又はチタニアゾルであり、該触媒担持スラリー中の該無機バインダーの固形分の含有量が、１〜１０重量％であり、
該触媒担持スラリーに含有される該有機バインダーが、アクリル系樹脂、ポリエステル系樹脂、ブタジエンラテックス、スチレン系樹脂、酢酸ビニル樹脂、ＳＢＲラテックス又はこれらのエマルジョンであり、該触媒担持スラリー中の該有機バインダーの固形分の含有量が、０．２〜８重量％である
ことを特徴とする金属ハニカム触媒ユニットの製造方法。A metal honeycomb catalyst unit that is dried after contacting a metal honeycomb carrier with a surface treatment liquid containing a hydrophilic resin binder and an inorganic binder and then contacting a catalyst, a catalyst-supporting slurry containing the inorganic binder and the organic binder. Is a manufacturing method of
The hydrophilic resin binder contained in the surface treatment liquid is a polyester resin, a polyvinyl acetate resin, a urea melamine resin, or an emulsion thereof, and the resin content of the hydrophilic resin binder in the surface treatment liquid Is 0.5 to 10% by weight,
The inorganic binder contained in the surface treatment liquid is alumina sol, colloidal silica or titania sol, and the solid content of the inorganic binder in the surface treatment liquid is 1 to 20% by weight,
The content of the catalyst contained in the catalyst-carrying slurry is 5 to 50% by weight,
The inorganic binder contained in the catalyst-carrying slurry is alumina sol, colloidal silica or titania sol, and the solid content of the inorganic binder in the catalyst-carrying slurry is 1 to 10% by weight,
The organic binder contained in the catalyst-carrying slurry is an acrylic resin, a polyester resin, a butadiene latex, a styrene resin, a vinyl acetate resin, an SBR latex, or an emulsion thereof, and the organic binder in the catalyst-carrying slurry The method for producing a metal honeycomb catalyst unit, wherein the solid content of the metal honeycomb catalyst unit is 0.2 to 8 wt% .
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