JP4378449B2 - Adsorbent and production method thereof - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、空気中のガス状汚染物質を除去する吸着材に関し、さらに詳しくは、アセトアルデヒドなどの低級脂肪族アルデヒドに対して、高い除去性能を持つ吸着材に関するものである。
【０００２】
【従来の技術】
室内や車内などの生活空間においては、悪臭や有害ガスなどの様々なガス状汚染物質が発生するが、生活環境の向上に伴い、これらガス状汚染物質を除去し、快適な生活環境を維持することに多くの関心が持たれており、空気清浄フィルターが使用されている。
【０００３】
シート状活性炭とは活性炭を含有するフェルトやペーパーであり、例示すると、活性炭素繊維のフェルトや活性炭素繊維や微粒状活性炭を湿式抄紙法でシート化したものや、微粒状活性炭シートを乾式法でシート化したものなどがあり、これらはプリーツ加工などをされて、ガス状汚染物質を除去する空気清浄フィルターとして使用されている。
【０００４】
生活空間で発生する主なガス状汚染物質としては、アンモニアを代表とする塩基性ガス、酢酸を代表とする酸性ガスやアセトアルデヒドなどの低級脂肪族アルデヒドがあげられる。これらのうち、アンモニアなどの塩基性ガスは鉱酸や有機酸をシート状活性炭に添着して中和反応により、また、酢酸やその他多くの有機ガス状汚染物質はシート状活性炭への物理吸着により除去されるが、アセトアルデヒドなどの低級脂肪族アルデヒドは他のガス状汚染物質に比べ除去が難しい物質である。
【０００５】
この課題に対して、低級脂肪族アルデヒドの除去性能を向上した吸着剤の検討がすすめられてきた。低級脂肪族アルデヒドは、アンモニア誘導体などの求核試薬の攻撃を受けて求核付加反応を起こすことが知られており、アミンが低級脂肪族アルデヒドの化学吸着に有効であることが推定でき、アミンやアミン塩を多孔質体に添着した吸着剤が種々提案されている。
【０００６】
特開昭５６−５３７４４号には活性炭にアニリンを添着した吸着剤、特開昭５６−５３７４４号には活性炭に塩酸ヒドロキシルアミンや硫酸ヒドロキシルアミンを添着した吸着剤、特開昭５９−１８６６４１号には活性炭にポリエチレンイミンを添着した吸着剤、特開昭６０−１３２６４５号には粘土鉱物にアニリン、トルイジン、メタニル酸（ｍ−アミノベンゼンスルホン酸）、スルファニル酸（ｐ−アミノベンゼンスルホン酸）やベンジルアミン及びその塩を担持した吸着剤、特開平７−１３６５０２号には活性炭素繊維にアミノベンゼンスルホン酸を添着した吸着剤が開示されている。
【０００７】
しかしながら、従来の吸着剤のうち、アニリン、塩酸ヒドロキシルアミン、硫酸ヒドロキシルアミン、ポリエチレンイミン、トルイジンやベンジルアミンを添着した吸着剤では、これらアミンが空気中の酸素や酸性ガスと反応し易く、これにより低級脂肪族アルデヒドの化学吸着作用の有効性が失われていくため、低級脂肪族アルデヒド除去性能の経時劣化が大きく、長期間の保存や使用に耐えないという問題がある。
【０００８】
また、アミノベンゼンスルホン酸を添着した吸着剤では、酸素や酸性ガスによる低級脂肪族アルデヒド除去性能の経時劣化こそ他のアミンを添着した吸着剤に比べて小さいものの、アミノベンゼンスルホン酸は水やアルコールなどの溶媒に対して難溶性であるため、極低濃度のアミノベンゼンスルホン酸添着溶液しか調整できず、その結果、シート状活性炭を添着溶液に浸漬したり、シート状活性炭に添着溶液を噴霧などしてもアミノベンゼンスルホン酸の添着量が多い吸着材を得ることは難しい。従って、高い低級脂肪族アルデヒド除去性能が得られないという問題がある。
【０００９】
【発明が解決しようとする課題】
そこで本発明の目的は、上記従来技術の有する問題点に鑑みて、低級脂肪族アルデヒドの除去性能が高く、酸素や酸性ガスによる低級脂肪族アルデヒドの除去性能の経時劣化が小さい吸着材及びその製造方法を提供することにある。
【００１０】
【課題を解決するための手段】
上記目的は、各請求項記載の発明により達成される。すなわち、本発明に係る吸着材の特徴構成は、シート状活性炭に、アミノベンゼンスルホン酸のアンモニウム塩が添着されていることにある。
【００１１】
一般に、シート状活性炭に薬剤を添着した吸着材は、薬剤を水やアルコールなどの適当な溶媒に溶解して添着溶液を調整し、シート状活性炭を添着溶液に浸漬した後乾燥する方法や、シート状活性炭に添着溶液を噴霧した後乾燥する方法により得られる。
【００１２】
ところが、前述したように、酸素や酸性ガスによる低級脂肪族アルデヒド除去性能の経時劣化が小さいアミノベンゼンスルホン酸は水に対して難溶性であり、また、アルコール、エーテル、ベンゼンなどに対しても難溶性であり、アミノベンゼンスルホン酸の添着溶液として十分な濃度が得られる適当な溶媒が見当たらず、アミノベンゼンスルホン酸のみを溶媒に加えて添着溶液を調整し、前記した方法でシート状活性炭に添着しても、短時間の処理ではアミノベンゼンスルホン酸の添着量が少なく、低級脂肪族アルデヒド除去性能の高い実用的な吸着材は得られない。
【００１３】
そこで、本発明者は低級脂肪族アルデヒドとの反応性が高く、酸素や酸性ガスによる低級脂肪族アルデヒド除去性能の経時劣化が小さい薬剤を求めて鋭意検討した結果、アミノベンゼンスルホン酸のアンモニウム塩を見出した。アミノベンゼンスルホン酸のアンモニウム塩は水溶性であるので、高濃度で溶解した添着溶液を調整することができ、この添着溶液を用いて前述したような浸漬法や噴霧法でシート状活性炭に添着すれば、アミノベンゼンスルホン酸のアンモニウム塩の添着量が多い吸着材が得られるのである。
【００１４】
その結果、低級脂肪族アルデヒドの除去性能が高く、かつ、低級脂肪族アルデヒド除去性能の経時劣化が小さい吸着材を提供することができる。
【００１５】
本発明に係る吸着材の製造方法の特徴構成は、アミノベンゼンスルホン酸のアンモニウム塩の水溶液をシート状活性炭に添着して製造することにある。
【００１６】
この構成によれば、酸素や酸性ガスによる低級脂肪族アルデヒド除去性能の経時劣化が小さいアミノベンゼンスルホン酸のアンモニウム塩の添着量を多くでき、これにより低級脂肪族アルデヒドの除去性能が高く、かつ低級脂肪族アルデヒド除去性能の経時劣化が小さい吸着材の製造方法を提供することができる。
【００１７】
加える前記アミノベンゼンスルホン酸のアンモニウム塩は水１００重量部に対して２〜５０重量部である。
【００１８】
アミノベンゼンスルホン酸のアンモニウム塩が水１００重量部に対して２重量部未満であると、低級脂肪族アルデヒドを除去するのに十分な量のアミノベンゼンスルホン酸のアンモニウム塩を多孔質体に添着することができず、また、５０重量部を越えて含ませても、量の増加に見合った効果が得られない。
【００１９】
【本発明の実施の形態】
本発明の実施の形態を以下に詳しく説明する。本実施形態に係る吸着材は、シート状活性炭に、アミノベンゼンスルホン酸のアンモニウム塩が添着されて構成されている。この吸着材は、アミノベンゼンスルホン酸のアンモニウム塩の水溶液をシート状活性炭に添着して製造される。
【００２０】
シート状活性炭とは、繊維状や微粒状の活性炭をフェルトやペーパーなどのシート状に成形したものであり、例示すると、活性炭素繊維のフェルトや活性炭素繊維や微粒状活性炭を湿式抄紙法でシート化したものや、微粒状活性炭シートを乾式法でシート化したものなどがある。
【００２１】
シート状活性炭の目付は３０〜１０００ｇ／ｍ2、好ましくは５０〜５００ｇ／ｍ2、より好ましくは１００〜２００ｇ／ｍ2であり、この範囲未満では、充分な吸着除去量が得られず、この範囲を超えると、シート状活性炭が厚くなってプリーツ加工などの加工がし難くなる。
【００２２】
シート状活性炭に含有される活性炭含有率は、３０〜１００重量％、好ましくは４０〜９０重量％、より好ましくは５０〜７０重量％である。この範囲未満では吸着除去性能が低く、この範囲を超えるとシートの強度が弱くなり、プリーツなどの加工性が劣る。
【００２３】
シート状活性炭に含有される活性炭の比表面積としては５００〜３０００ｍ2／ｇ、好ましくは７００〜３０００ｍ2/ｇ、より好ましくは１０００〜３０００ｍ2／ｇであり、比表面積の大きな活性炭を使用した方が、低級脂肪族アルデヒドとの反応に有効な面積を大きくすることができ、高い低級脂肪族アルデヒド除去性能が得られる。
【００２４】
シート状活性炭へのアミノベンゼンスルホン酸のアンモニウム塩の添着量としては、活性炭１ｇ当たりに０．０３〜０．３ｇ、好ましくは０．０５〜０．２５ｇ、さらに好ましくは０．１〜０．２ｇである。この範囲未満では、高い低級アルデヒド除去性能が得られず、この範囲を超えて添着してもアルデヒド除去性能は向上しない。
【００２５】
アミノベンゼンスルホン酸のアンモニウム塩は、アミノベンゼンスルホン酸とアンモニアとの反応生成物として得ることができ、アミノベンゼンスルホン酸のアンモニウム塩の添着溶液は、あらかじめアミノベンゼンスルホン酸とアンモニアとの反応生成物として得たものを水に溶解したり、アンモニア水にアミノベンゼンスルホン酸を加えたり、水にアミノベンゼンスルホン酸と炭酸アンモニウムや炭酸水素アンモニウムあるいはカルバミド酸アンモニウムなどのアンモニウム塩を加えたりして調整できる。
【００２６】
添着溶液中のアミノベンゼンスルホン酸のアンモニウム塩は、水１００重量部に対して２〜５０重量部、好ましくは４〜３０重量部、より好ましくは５〜２０重量部である。この範囲未満では、シート状活性炭へのアミノベンゼンスルホン酸のアンモニウム塩の添着量が少なくなって、低級脂肪族アルデヒド除去性能の高い吸着材が得難く、また、この範囲を越えた添着溶液を使用しても、低級脂肪族アルデヒド除去性能が大きく向上しない。
【００２７】
アミノベンゼンスルホン酸にはｏ−アミノベンゼンスルホン酸、ｍ−アミノベンゼンスルホン酸、ｐ−アミノベンゼンスルホン酸の３つの異性体があり、これらのいずれのアンモニウム塩も使用できるが、ｐ−アミノベンゼンスルホン酸のアンモニウム塩が低級脂肪族アルデヒドとの反応性が強く特に好ましい。
【００２８】
本発明の吸着材には、アミノベンゼンスルホン酸のアンモニウム塩以外に、リンゴ酸、クエン酸などの低級脂肪族アルデヒド以外のガス成分と反応する薬剤や抗菌性を持たせるための抗菌剤などの薬剤をさらに添着することができる。しかし、この場合には、アミノベンゼンスルホン酸のアンモニウム塩の低級脂肪族アルデヒドとの反応性を著しく低下させないように、薬剤や添着法を選択する必要がある。また、本発明の吸着材は、単独で使用するだけでなく、他の除塵濾材などと積層一体化したりして使用することができる。
【００２９】
以下に実施例をあげて、本発明をさらに詳しく説明するが、本発明はこれら実施例に限定されるものではない。
【００３０】
【実施例】
まず、本実施例で用いた吸着材の試験方法を以下に示す。
【００３１】
（１）アルデヒド除去性能
シート状活性炭の吸着材を直径９０ｍｍの円板に打ち抜き、濾過面積４５．３ｃｍ2のフィルターホルダーに装着した。温度２５℃、相対湿度５０％に調整した３０ｐｐｍのアセトアルデヒドを含む空気を風量５Ｌ／ｍｉｎでフィルターホルダーに供給した。フィルターホルダーの出口のアセトアルデヒド濃度を７分ごとに測定し、除去率（η［−］）を次式にアセトアルデヒド入口濃度（Ｃｉ［ｐｐｍ］）、アセトアルデヒド出口濃度（Ｃｏ［ｐｐｍ］）を代入して算出した。なお、アセトアルデヒド濃度はＦＩＤ付きガスクロマトグラフで測定した。
【００３２】
【数１】
この除去率が１０％に低下するまで試験を継続し、この試験中に７分毎に測定したフィルターホルダー出口のアセトアルデヒド濃度から算出した除去率と、フィルターホルダーの入口のアセトアルデヒド濃度および風量から７分毎のアセトアルデヒド吸着量を求め、それらを積算して濾過面積で除して、吸着容量とした。この吸着容量により、吸着材のアルデヒド除去性能を評価した。
【００３４】
（２）劣化処理後のアルデヒド除去性能
シート状活性炭吸着材のアルデヒド除去性能の経時劣化をみるため、劣化処理による加速試験を行った。ここで、劣化処理とはシート状活性炭吸着材を８０℃の雰囲気下で１５０時間放置することであり、この劣化処理は、２０℃の雰囲気下で約１年の保管期間に相当する。劣化処理を行ったシート状活性炭吸着材について、（１）のアルデヒド除去性能試験を行い、吸着容量を求めてアルデヒド除去性能を評価した。
【００３５】
（実施例１）
濃度２．８重量％のアンモニア水１００重量部にｐ−アミノベンゼンスルホン酸２５重量部を加えた後、水分を蒸発させて反応生成物であるｐ−アミノベンゼンスルホン酸のアンモニウム塩を得た。水９８ｇにこのｐ−アミノベンゼンスルホン酸のアンモニウム塩２ｇを加えて添着溶液を調整した。この添着溶液に、粒径３００μｍで比表面積１０５０ｍ2／ｇの微粒状ヤシガラ活性炭を補強繊維としてレーヨン繊維，ポリエステル系熱融着繊維，ポリビニルアルコール繊維およびバインダーとして粉末ポリビニルアルコールとともに湿式抄紙法でシート化した活性炭ペーパー（目付２８５ｇ／ｍ2，活性炭含有率７０重量％）を１分間浸漬して取り出した後、８０℃の熱風乾燥機中で３時間乾燥して吸着材を作製した。得られた吸着材の薬剤添着量は１９ｇ／ｍ2であった。
【００３６】
（実施例２）
水９５ｇに実施例１で得たｐ−アミノベンゼンスルホン酸のアンモニウム塩５ｇを加えて添着溶液を調整した。この添着溶液に、実施例１で用いたものと同じ活性炭ペーパーを１分間浸漬して取り出した後、８０℃の熱風乾燥機中で３時間乾燥して吸着材を作製した。得られた吸着材の薬剤添着量は３８ｇ／ｍ2であった。
【００３７】
（実施例３）
水９０ｇに実施例１で得たｐ−アミノベンゼンスルホン酸のアンモニウム塩１０ｇを加えて添着溶液を調整した。この添着溶液に、実施例１で用いたものと同じ活性炭ペーパーを１分間浸漬して取り出した後、８０℃の熱風乾燥機中で３時間乾燥して吸着材を作製した。得られた吸着材の薬剤添着量は６４ｇ／ｍ2であった。
【００３８】
（比較例１）
水９８ｇにｐ−アミノベンゼンスルホン酸２ｇを加えて添着溶液を調整した。この添着溶液に、実施例１で用いたものと同じ活性炭ペーパーを１分間浸漬して取り出した後、８０℃の熱風乾燥機中で３時間乾燥して吸着材を作製した。得られた吸着材の薬剤添着量は１１ｇ／ｍ2であった。
【００３９】
（比較例２）
水９５ｇにｐ−アミノベンゼンスルホン酸５ｇを加えて添着溶液を調整した。この添着溶液に、実施例１で用いたものと同じ活性炭ペーパーを１分間浸漬して取り出した後、８０℃の熱風乾燥機中で３時間乾燥して吸着材を作製した。得られた吸着材の薬剤添着量は１０ｇ／ｍ2であった。
【００４０】
（比較例３）
水９０ｇにｐ−アミノベンゼンスルホン酸１０ｇを加えて添着溶液を調整した。この添着溶液に、実施例１で用いたものと同じ活性炭ペーパーを１分間浸漬して取り出した後、８０℃の熱風乾燥機中で３時間乾燥して吸着材を作製した。得られた吸着材の薬剤添着量は１２ｇ／ｍ2であった。
【００４１】
（比較例４）
水９５ｇに２−アミノエタノール５ｇを加えて添着溶液を調整した。この添着溶液に、実施例１で用いたものと同じ活性炭ペーパーを１分間浸漬して取り出した後、８０℃の熱風乾燥機中で３時間乾燥して吸着材を作製した。得られた吸着材の薬剤添着量は３１ｇ／ｍ2であった。
【００４２】
（比較例５）
水９５ｇにモルホリン５ｇを加えて添着溶液を調整した。この添着溶液に、実施例１で用いたものと同じ活性炭ペーパーを１分間浸漬して取り出した後、８０℃の熱風乾燥機中で３時間乾燥して吸着材を作製した。得られた吸着材の薬剤添着量は３３ｇ／ｍ2であった。
【００４３】
（実施例４）
水９８ｇに実施例１で得たｐ−アミノベンゼンスルホン酸のアンモニウム塩２ｇを加えて添着溶液を調整した。この添着溶液に、繊維径２０μｍで比表面積１４５０ｍ2／ｇの活性炭素繊維フェルト（目付２００ｇ／ｍ2，活性炭含有率１００重量％）を１分間浸漬して取り出した後、８０℃の熱風乾燥機中で３時間乾燥して吸着材を作製した。得られた吸着材の薬剤添着量は２６ｇ／ｍ2であった。
【００４４】
（実施例５）
水９５ｇに実施例１で得たｐ−アミノベンゼンスルホン酸のアンモニウム塩５ｇを加えて添着溶液を調整した。この添着溶液に、実施例４で用いたものと同じ活性炭素繊維フェルトを１分間浸漬して取り出した後、８０℃の熱風乾燥機中で３時間乾燥して吸着材を作製した。得られた吸着材の薬剤添着量は４９ｇ／ｍ2であった。
【００４５】
（実施例６）
水９０ｇに実施例１で得たｐ−アミノベンゼンスルホン酸のアンモニウム塩１０ｇを加えて添着溶液を調整した。この添着溶液に、実施例４で用いたものと同じ活性炭素繊維フェルトを１分間浸漬して取り出した後、８０℃の熱風乾燥機中で３時間乾燥して吸着材を作製した。得られた吸着材の薬剤添着量は８３ｇ／ｍ2であった。
【００４６】
（比較例６）
水９８ｇにｐ−アミノベンゼンスルホン酸２ｇを加えて添着溶液を調整した。この添着溶液に、実施例４で用いたものと同じ活性炭素繊維フェルトを１分間浸漬して取り出した後、８０℃の熱風乾燥機中で３時間乾燥して吸着材を作製した。得られた吸着材の薬剤添着量は１３ｇ／ｍ2であった。
【００４７】
（比較例７）
水９５ｇにｐ−アミノベンゼンスルホン酸５ｇを加えて添着溶液を調整した。この添着溶液に、実施例４で用いたものと同じ活性炭素繊維フェルトを１分間浸漬して取り出した後、８０℃の熱風乾燥機中で３時間乾燥して吸着材を作製した。得られた吸着材の薬剤添着量は１３ｇ／ｍ2であった。
【００４８】
（比較例８）
水９０ｇにｐ−アミノベンゼンスルホン酸１０ｇを加えて添着溶液を調整した。この添着溶液に、実施例４で用いたものと同じ活性炭素繊維フェルトを１分間浸漬して取り出した後、８０℃の熱風乾燥機中で３時間乾燥して吸着材を作製した。得られた吸着材の薬剤添着量は１２ｇ／ｍ2であった。
【００４９】
上記吸着材について、先に説明した方法により劣化処理前のアルデヒド除去性能と劣化処理後のアルデヒド除去性能を測定した。結果を表１に示す。
【００５０】
【表１】
ｐ−アミノベンゼンスルホン酸をシート状活性炭に添着した比較例１〜３および７〜９は、劣化処理によるアルデヒド除去性能の低下は小さいが、ｐ−アミノベンゼンスルホン酸が水難溶性であるため、添着液へのｐ−アミノベンゼンスルホン酸の添加量を増やしても高い溶解濃度の添着液にならず添着量が増えないため、アルデヒド除去性能が低い。また、２−アミノエタノール、モルホリンを活性炭に添着した比較例４，５は、劣化処理前のアルデヒド除去性能は高いが、劣化処理後のアルデヒド除去性能の低下が大きい。
【００５２】
これらに対して、ｐ−アミノベンゼンスルホン酸のアンモニウム塩を添着した実施例１〜６は、高いアルデヒド除去性能を持つとともに、劣化処理によるアルデヒド除去性能の低下も小さいことがわかる。
【００５３】
【発明の効果】
以上説明したように、本発明によれば、低級脂肪族アルデヒドの除去性能が高く、かつ低級脂肪族アルデヒド除去性能の経時劣化が小さいシート状活性炭の吸着材およびその製造方法を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an adsorbent that removes gaseous pollutants in the air, and more particularly to an adsorbent that has high removal performance for lower aliphatic aldehydes such as acetaldehyde.
[0002]
[Prior art]
Various gaseous pollutants such as bad odors and harmful gases are generated in living spaces such as indoors and cars. With the improvement of the living environment, these gaseous pollutants are removed to maintain a comfortable living environment. Of particular interest is the use of air cleaning filters.
[0003]
Sheet activated carbon is felt or paper containing activated carbon. For example, activated carbon fiber felt or activated carbon fiber or fine activated carbon is formed into a sheet by a wet papermaking method, or a fine activated carbon sheet is dried by a dry method. Some of them are made into sheets, and these are pleated and used as air purification filters to remove gaseous pollutants.
[0004]
Examples of main gaseous pollutants generated in living spaces include basic gases typified by ammonia, acidic gases typified by acetic acid, and lower aliphatic aldehydes such as acetaldehyde. Of these, basic gases such as ammonia are applied by neutralization reaction with mineral acid or organic acid added to the sheet-like activated carbon, and acetic acid and many other organic gaseous pollutants are obtained by physical adsorption on the sheet-like activated carbon. Although removed, lower aliphatic aldehydes such as acetaldehyde are more difficult to remove than other gaseous pollutants.
[0005]
In order to solve this problem, studies have been made on an adsorbent having improved lower aliphatic aldehyde removal performance. Lower aliphatic aldehydes are known to undergo nucleophilic addition reactions upon attack by nucleophilic reagents such as ammonia derivatives, and it can be assumed that amines are effective for chemisorption of lower aliphatic aldehydes. And various adsorbents in which an amine salt is attached to a porous body have been proposed.
[0006]
JP-A 56-53744 discloses an adsorbent obtained by adding aniline to activated carbon, JP-A 56-53744 discloses an adsorbent obtained by adding hydroxylamine hydrochloride or hydroxylamine to activated carbon, and JP-A 59-186642. Is an adsorbent in which activated carbon is impregnated with polyethyleneimine. JP-A-60-132645 discloses clay minerals such as aniline, toluidine, metanilic acid (m-aminobenzenesulfonic acid), sulfanilic acid (p-aminobenzenesulfonic acid) and benzyl. An adsorbent carrying an amine and a salt thereof, and JP-A-7-136502 discloses an adsorbent in which aminobenzenesulfonic acid is impregnated with activated carbon fiber.
[0007]
However, among the conventional adsorbents, those adsorbed with aniline, hydroxylamine hydrochloride, hydroxylamine sulfate, polyethyleneimine, toluidine, and benzylamine tend to react with oxygen and acid gases in the air. Since the effectiveness of the chemical adsorption action of the lower aliphatic aldehyde is lost, there is a problem that the lower aliphatic aldehyde removal performance is greatly deteriorated with time and cannot be stored or used for a long time.
[0008]
Moreover, in the adsorbent adsorbed with aminobenzenesulfonic acid, although the deterioration with time of the lower aliphatic aldehyde removal performance by oxygen or acid gas is smaller than the adsorbent adsorbed with other amines, aminobenzenesulfonic acid is water or alcohol. Because it is sparingly soluble in such solvents, it is possible to adjust only an aminobenzene sulfonic acid additive solution with a very low concentration. As a result, the sheet-like activated carbon is immersed in the additive solution, or the additive solution is sprayed on the sheet-like activated carbon. Even so, it is difficult to obtain an adsorbent with a large amount of aminobenzenesulfonic acid. Therefore, there is a problem that high lower aliphatic aldehyde removal performance cannot be obtained.
[0009]
[Problems to be solved by the invention]
Therefore, in view of the above-mentioned problems of the prior art, the object of the present invention is an adsorbent having a high lower aliphatic aldehyde removal performance and a low degradation with time of the lower aliphatic aldehyde removal performance by oxygen or acid gas, and its production It is to provide a method.
[0010]
[Means for Solving the Problems]
The above object can be achieved by the inventions described in the claims. That is, the characteristic configuration of the adsorbent according to the present invention is that an ammonium salt of aminobenzenesulfonic acid is attached to the sheet-like activated carbon.
[0011]
In general, an adsorbent in which a drug is attached to sheet-like activated carbon is prepared by dissolving the drug in an appropriate solvent such as water or alcohol to prepare an adhesion solution, immersing the sheet-like activated carbon in the adhesion solution, and drying the sheet. It can be obtained by spraying the impregnating solution on the activated carbon and then drying it.
[0012]
However, as described above, aminobenzene sulfonic acid, which has a low degradation with time of lower aliphatic aldehyde removal performance by oxygen or acid gas, is poorly soluble in water and difficult for alcohol, ether, benzene, and the like. There is no suitable solvent that is soluble and sufficient concentration can be obtained as an aminobenzenesulfonic acid addition solution, and only the aminobenzenesulfonic acid is added to the solvent to prepare the attachment solution. Even in a short time treatment, however, the amount of aminobenzenesulfonic acid attached is small, and a practical adsorbent with high lower aliphatic aldehyde removal performance cannot be obtained.
[0013]
Therefore, as a result of intensive investigations for an agent having high reactivity with lower aliphatic aldehydes and low degradation with time of lower aliphatic aldehyde removal performance by oxygen or acid gas, the present inventor obtained an ammonium salt of aminobenzenesulfonic acid. I found it. Since the ammonium salt of aminobenzene sulfonic acid is water-soluble, it is possible to prepare an additive solution dissolved at a high concentration, and this additive solution can be attached to sheet-like activated carbon by the dipping method or spray method as described above. For example, an adsorbent with a large amount of aminobenzenesulfonic acid ammonium salt attached can be obtained.
[0014]
As a result, it is possible to provide an adsorbent that has a high lower aliphatic aldehyde removal performance and a low degradation with time of the lower aliphatic aldehyde removal performance.
[0015]
A characteristic configuration of the method for producing an adsorbent according to the present invention is that an aqueous solution of an ammonium salt of aminobenzenesulfonic acid is attached to a sheet-like activated carbon.
[0016]
According to this configuration, it is possible to increase the amount of aminobenzene sulfonic acid ammonium salt that is less deteriorated over time in the ability to remove lower aliphatic aldehydes by oxygen or acidic gas, thereby reducing the lower aliphatic aldehyde removal performance. It is possible to provide a method for producing an adsorbent having a small degradation with time of the aliphatic aldehyde removal performance.
[0017]
The ammonium salt of aminobenzenesulfonic acid added is 2 to 50 parts by weight with respect to 100 parts by weight of water.
[0018]
When the ammonium salt of aminobenzene sulfonic acid is less than 2 parts by weight with respect to 100 parts by weight of water, a sufficient amount of ammonium salt of aminobenzene sulfonic acid is attached to the porous body to remove the lower aliphatic aldehyde. In addition, even if it exceeds 50 parts by weight, an effect commensurate with the increase in amount cannot be obtained.
[0019]
[Embodiments of the Invention]
Embodiments of the present invention will be described in detail below. The adsorbent according to the present embodiment is configured by adhering an ammonium salt of aminobenzenesulfonic acid to a sheet-like activated carbon. This adsorbent is produced by attaching an aqueous solution of an aminobenzenesulfonic acid ammonium salt to a sheet-like activated carbon.
[0020]
The sheet-like activated carbon is obtained by forming fibrous or fine granular activated carbon into a sheet shape such as felt or paper. For example, activated carbon fiber felt, activated carbon fiber or fine granular activated carbon is sheeted by a wet papermaking method. And those obtained by making a granular activated carbon sheet into a sheet by a dry method.
[0021]
The basis weight of the sheet-like activated carbon is 30 to 1000 g / m 2 , preferably 50 to 500 g / m 2 , more preferably 100 to 200 g / m 2 , and if it is less than this range, a sufficient adsorption removal amount cannot be obtained. When the range is exceeded, the sheet-like activated carbon becomes thick and it becomes difficult to perform processing such as pleating.
[0022]
The activated carbon content contained in the sheet-like activated carbon is 30 to 100% by weight, preferably 40 to 90% by weight, and more preferably 50 to 70% by weight. If it is less than this range, the adsorption removal performance is low, and if it exceeds this range, the strength of the sheet becomes weak and the workability of pleats and the like is poor.
[0023]
500~3000m 2 / g as a specific surface area of the activated carbon contained in the sheet-like activated carbon is preferably 700~3000m 2 / g, more preferably 1000~3000m 2 / g, better to use a large activated carbon having a specific surface area of However, the effective area for the reaction with the lower aliphatic aldehyde can be increased, and high lower aliphatic aldehyde removal performance can be obtained.
[0024]
The amount of the aminobenzenesulfonic acid ammonium salt attached to the sheet-like activated carbon is 0.03 to 0.3 g, preferably 0.05 to 0.25 g, more preferably 0.1 to 0.2 g, per 1 g of activated carbon. It is. If it is less than this range, a high lower aldehyde removal performance cannot be obtained, and even if it is added beyond this range, the aldehyde removal performance is not improved.
[0025]
Ammonium salt of aminobenzene sulfonic acid can be obtained as a reaction product of aminobenzene sulfonic acid and ammonia, and an ammonium salt of aminobenzene sulfonic acid is added in advance as a reaction product of aminobenzene sulfonic acid and ammonia. Can be prepared by dissolving in water, adding aminobenzenesulfonic acid to aqueous ammonia, or adding ammonium salt such as aminobenzenesulfonic acid and ammonium carbonate, ammonium hydrogen carbonate or ammonium carbamate to water. .
[0026]
The ammonium salt of aminobenzenesulfonic acid in the impregnating solution is 2 to 50 parts by weight, preferably 4 to 30 parts by weight, more preferably 5 to 20 parts by weight with respect to 100 parts by weight of water. Below this range, the amount of aminobenzenesulfonic acid ammonium salt adhering to the sheet-like activated carbon becomes small, making it difficult to obtain an adsorbent with high performance for removing lower aliphatic aldehydes. However, the lower aliphatic aldehyde removal performance is not greatly improved.
[0027]
There are three isomers of aminobenzenesulfonic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, and p-aminobenzenesulfonic acid, and any of these ammonium salts can be used. Acid ammonium salts are particularly preferred because of their strong reactivity with lower aliphatic aldehydes.
[0028]
In addition to the ammonium salt of aminobenzene sulfonic acid, the adsorbent of the present invention includes agents that react with gas components other than lower aliphatic aldehydes such as malic acid and citric acid, and agents such as antibacterial agents for imparting antibacterial properties. Can be further attached. However, in this case, it is necessary to select a chemical and an attachment method so as not to significantly reduce the reactivity of the ammonium salt of aminobenzenesulfonic acid with the lower aliphatic aldehyde. In addition, the adsorbent of the present invention can be used not only independently but also laminated and integrated with other dust removing filter media.
[0029]
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
[0030]
【Example】
First, the test method of the adsorbent used in this example is shown below.
[0031]
(1) Aldehyde removal performance An adsorbent of activated carbon in sheet form was punched into a 90 mm diameter disc and mounted on a filter holder with a filtration area of 45.3 cm 2 . Air containing 30 ppm acetaldehyde adjusted to a temperature of 25 ° C. and a relative humidity of 50% was supplied to the filter holder at a flow rate of 5 L / min. Measure the acetaldehyde concentration at the outlet of the filter holder every 7 minutes, and substitute the acetaldehyde inlet concentration (Ci [ppm]) and the acetaldehyde outlet concentration (Co [ppm]) for the removal rate (η [−]) into the following equation: Calculated. The acetaldehyde concentration was measured by a gas chromatograph with FID.
[0032]
[Expression 1]
The test was continued until the removal rate dropped to 10%, and the removal rate calculated from the acetaldehyde concentration at the filter holder outlet measured every 7 minutes during the test, and 7 minutes from the acetaldehyde concentration and air volume at the filter holder inlet. The amount of acetaldehyde adsorbed for each was determined, and these were integrated and divided by the filtration area to obtain the adsorption capacity. Based on this adsorption capacity, the aldehyde removal performance of the adsorbent was evaluated.
[0034]
(2) Aldehyde removal performance after deterioration treatment In order to see the deterioration over time of the aldehyde removal performance of the sheet-like activated carbon adsorbent, an accelerated test was conducted by the deterioration treatment. Here, the deterioration treatment is to leave the sheet-like activated carbon adsorbent for 150 hours in an atmosphere at 80 ° C., and this deterioration treatment corresponds to a storage period of about 1 year in an atmosphere at 20 ° C. About the sheet-like activated carbon adsorbent which performed the degradation process, the aldehyde removal performance test of (1) was done, adsorption capacity was calculated | required, and the aldehyde removal performance was evaluated.
[0035]
Example 1
After adding 25 parts by weight of p-aminobenzenesulfonic acid to 100 parts by weight of ammonia water having a concentration of 2.8% by weight, water was evaporated to obtain an ammonium salt of p-aminobenzenesulfonic acid as a reaction product. 2 g of this ammonium salt of p-aminobenzenesulfonic acid was added to 98 g of water to prepare an adhesion solution. This impregnated solution is formed into a sheet by a wet papermaking method together with rayon fibers, polyester heat-bonding fibers, polyvinyl alcohol fibers as binder fibers and fine polyvinyl alcohol fibers as binders with a particle size of 300 μm and a specific surface area of 1050 m 2 / g as a reinforcing fiber. The obtained activated carbon paper (weight per unit area 285 g / m 2 , activated carbon content 70% by weight) was immersed for 1 minute and taken out, and then dried in a hot air dryer at 80 ° C. for 3 hours to prepare an adsorbent. The adsorbent thus obtained had a chemical adhering amount of 19 g / m 2 .
[0036]
(Example 2)
An impregnation solution was prepared by adding 5 g of ammonium salt of p-aminobenzenesulfonic acid obtained in Example 1 to 95 g of water. The same activated carbon paper as used in Example 1 was immersed in this attachment solution for 1 minute and then taken out, and then dried in a hot air dryer at 80 ° C. for 3 hours to prepare an adsorbent. The adsorbent thus obtained had a chemical adhering amount of 38 g / m 2 .
[0037]
(Example 3)
An addition solution was prepared by adding 10 g of ammonium salt of p-aminobenzenesulfonic acid obtained in Example 1 to 90 g of water. The same activated carbon paper as used in Example 1 was immersed in this attachment solution for 1 minute and then taken out, and then dried in a hot air dryer at 80 ° C. for 3 hours to prepare an adsorbent. The resulting adsorbent had a drug loading of 64 g / m 2 .
[0038]
(Comparative Example 1)
2 g of p-aminobenzenesulfonic acid was added to 98 g of water to prepare an impregnation solution. The same activated carbon paper as used in Example 1 was immersed in this attachment solution for 1 minute and then taken out, and then dried in a hot air dryer at 80 ° C. for 3 hours to prepare an adsorbent. The adsorbent thus obtained had a chemical adhering amount of 11 g / m 2 .
[0039]
(Comparative Example 2)
An impregnation solution was prepared by adding 5 g of p-aminobenzenesulfonic acid to 95 g of water. The same activated carbon paper as used in Example 1 was immersed in this attachment solution for 1 minute and then taken out, and then dried in a hot air dryer at 80 ° C. for 3 hours to prepare an adsorbent. The adsorbent thus obtained had a chemical adhering amount of 10 g / m 2 .
[0040]
(Comparative Example 3)
An addition solution was prepared by adding 10 g of p-aminobenzenesulfonic acid to 90 g of water. The same activated carbon paper as used in Example 1 was immersed in this attachment solution for 1 minute and then taken out, and then dried in a hot air dryer at 80 ° C. for 3 hours to prepare an adsorbent. The adsorbent thus obtained had a chemical adhering amount of 12 g / m 2 .
[0041]
(Comparative Example 4)
An adhesion solution was prepared by adding 5 g of 2-aminoethanol to 95 g of water. The same activated carbon paper as used in Example 1 was immersed in this attachment solution for 1 minute and then taken out, and then dried in a hot air dryer at 80 ° C. for 3 hours to prepare an adsorbent. The obtained adsorbent had a chemical adhering amount of 31 g / m 2 .
[0042]
(Comparative Example 5)
An impregnating solution was prepared by adding 5 g of morpholine to 95 g of water. The same activated carbon paper as used in Example 1 was immersed in this attachment solution for 1 minute and then taken out, and then dried in a hot air dryer at 80 ° C. for 3 hours to prepare an adsorbent. The obtained adsorbent had a chemical adhering amount of 33 g / m 2 .
[0043]
(Example 4)
An addition solution was prepared by adding 2 g of ammonium salt of p-aminobenzenesulfonic acid obtained in Example 1 to 98 g of water. This impregnation solution, a fiber diameter of 20μm specific surface area 1450 m 2 / g of the active carbon fiber felt (basis weight 200 g / m 2, the activated carbon content of 100 wt%) was immersed in a take-out 1 minute, 80 ° C. hot air dryer The adsorbent was prepared by drying for 3 hours. The adsorbent thus obtained had a chemical adhering amount of 26 g / m 2 .
[0044]
(Example 5)
An impregnation solution was prepared by adding 5 g of ammonium salt of p-aminobenzenesulfonic acid obtained in Example 1 to 95 g of water. The same activated carbon fiber felt as that used in Example 4 was immersed in this impregnation solution for 1 minute and then taken out, followed by drying in a hot air dryer at 80 ° C. for 3 hours to produce an adsorbent. The adsorbent thus obtained had a drug loading of 49 g / m 2 .
[0045]
(Example 6)
An addition solution was prepared by adding 10 g of ammonium salt of p-aminobenzenesulfonic acid obtained in Example 1 to 90 g of water. The same activated carbon fiber felt as that used in Example 4 was immersed in this impregnation solution for 1 minute and then taken out, followed by drying in a hot air dryer at 80 ° C. for 3 hours to produce an adsorbent. The obtained adsorbent had a chemical adhering amount of 83 g / m 2 .
[0046]
(Comparative Example 6)
2 g of p-aminobenzenesulfonic acid was added to 98 g of water to prepare an impregnation solution. The same activated carbon fiber felt as that used in Example 4 was immersed in this impregnation solution for 1 minute and then taken out, followed by drying in a hot air dryer at 80 ° C. for 3 hours to produce an adsorbent. The adsorbent thus obtained had a chemical adhering amount of 13 g / m 2 .
[0047]
(Comparative Example 7)
An impregnation solution was prepared by adding 5 g of p-aminobenzenesulfonic acid to 95 g of water. The same activated carbon fiber felt as that used in Example 4 was immersed in this impregnation solution for 1 minute and then taken out, followed by drying in a hot air dryer at 80 ° C. for 3 hours to produce an adsorbent. The adsorbent thus obtained had a chemical adhering amount of 13 g / m 2 .
[0048]
(Comparative Example 8)
An addition solution was prepared by adding 10 g of p-aminobenzenesulfonic acid to 90 g of water. The same activated carbon fiber felt as that used in Example 4 was immersed in this impregnation solution for 1 minute and then taken out, followed by drying in a hot air dryer at 80 ° C. for 3 hours to produce an adsorbent. The adsorbent thus obtained had a chemical adhering amount of 12 g / m 2 .
[0049]
About the said adsorbent, the aldehyde removal performance before deterioration processing and the aldehyde removal performance after deterioration processing were measured by the method demonstrated previously. The results are shown in Table 1.
[0050]
[Table 1]
In Comparative Examples 1 to 3 and 7 to 9 in which p-aminobenzenesulfonic acid is attached to sheet-like activated carbon, the degradation of the aldehyde removal performance due to the deterioration treatment is small, but p-aminobenzenesulfonic acid is poorly water-soluble. Even if the amount of p-aminobenzene sulfonic acid added to the solution is increased, the addition solution does not increase at a high dissolution concentration, and the amount of addition does not increase, so the aldehyde removal performance is low. Moreover, Comparative Examples 4 and 5 in which 2-aminoethanol and morpholine are impregnated with activated carbon have a high aldehyde removal performance before the deterioration treatment, but a large decrease in the aldehyde removal performance after the deterioration treatment.
[0052]
On the other hand, it can be seen that Examples 1 to 6 to which an ammonium salt of p-aminobenzenesulfonic acid is attached have a high aldehyde removal performance and a small decrease in the aldehyde removal performance due to the deterioration treatment.
[0053]
【The invention's effect】
As described above, according to the present invention, it is possible to provide a sheet-like activated carbon adsorbent having a high lower aliphatic aldehyde removal performance and a low degradation with time of the lower aliphatic aldehyde removal performance, and a method for producing the same. .
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002043510A JP4378449B2 (en) | 2002-02-20 | 2002-02-20 | Adsorbent and production method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002043510A JP4378449B2 (en) | 2002-02-20 | 2002-02-20 | Adsorbent and production method thereof |
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| KR100718060B1 (en) * | 2006-09-13 | 2007-05-14 | 이더블유에스 코리아 주식회사 | An apparatus and power-transmitting method of belt type turret |
| JP2017029389A (en) * | 2015-07-31 | 2017-02-09 | パナソニックエコシステムズ株式会社 | filter |
| CN114073935A (en) * | 2015-10-22 | 2022-02-22 | 格瑞福技术有限公司 | Treated activated carbon for removal of organic and inorganic contaminants from air |
| JP7288647B2 (en) * | 2018-11-14 | 2023-06-08 | ユニチカ株式会社 | filter |
| JP6511557B1 (en) * | 2018-02-28 | 2019-05-15 | ユニチカ株式会社 | Wet mixed sheet for air cleaning |
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| JPH09239267A (en) * | 1996-03-08 | 1997-09-16 | Osaka Gas Co Ltd | Method for application of spreader to active carbon fiber paper |
| JP3545888B2 (en) * | 1996-09-30 | 2004-07-21 | 株式会社神戸製鋼所 | Deodorizing filter |
| JP3783819B2 (en) * | 1998-10-09 | 2006-06-07 | 東洋紡績株式会社 | Air purification filter |
| JP4068759B2 (en) * | 1999-05-21 | 2008-03-26 | 株式会社神戸製鋼所 | Air purifier |
| JP4507296B2 (en) * | 1999-06-18 | 2010-07-21 | 株式会社豊田中央研究所 | Deodorizing material |
| JP2001029443A (en) * | 1999-07-15 | 2001-02-06 | Kobe Steel Ltd | Deodorizing filter and method for removing lower aliphatic aldehyde in atmosphere |
| JP2003093872A (en) * | 2001-09-21 | 2003-04-02 | Toyobo Co Ltd | Adsorbent and its preparing method |
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