JP2004025023A - Active carbon carrier, catalyst-carrying active carbons, and method of producing them - Google Patents
Active carbon carrier, catalyst-carrying active carbons, and method of producing them Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、金属触媒を担持するための繊維状活性炭および金属触媒を担持した繊維状活性炭に関し、より詳細には、高分子固体電解質燃料電池の電極に使用され、水素化および脱水素化反応に用いられる活性炭担体および触媒担持活性炭に関する。
【０００２】
たとえば、ベンゼン、トルエン、キシレン、メシチレンなどの単環芳香族化合物、ナフタレン、メチルナフタレンなどの２環芳香族化合物およびアントラセンなどの３環芳香族化合物を水素化するシステム、あるいは水素化物であるシクロヘキサン、メチルシクロヘキサン、ジメチルシクロヘキサンなどの単環水素化芳香族化合物、テトラリン、デカリン、メチルデカリンなどの２環水素化芳香族化合物、およびテトラデカヒドロアントラセン、テトラデカヒドロメチルアントラセンなどの３環水素化芳香族化合物を脱水素するシステムなどに用いられる活性炭担体および触媒担持活性炭に関するものである。
【０００３】
【従来の技術】
従来、触媒を担持する担体としては、表面積が大きく、耐薬品性の高い粒状活性炭、活性炭ペーパーなどが用いられている。たとえば、水素化物を脱水素するシステムに用いられる触媒担体は、脱水素反応が吸熱反応であるので、反応促進のために４００℃までの雰囲気にする必要があり、したがって熱伝導性に優れ、かつ水素ガスや芳香族化合物などの生成物の拡散性にも優れていることを求められるが、十分な性能は得られていなかった。
【０００４】
たとえば、特開２００１−１１０４３７には、常温で液体の水素化芳香族化合物原料から加熱した脱水素触媒反応装置により水素を生成、分離し、燃料電池に水素を供給するシステムが考案されている。このシステムではＣＯ、ＣＯ２などの副生成物を生じることなく、高純度水素を効率よく製造、供給することができ、システムのコンパクト化ができる特徴を有する。
【０００５】
上記公報では触媒として活性成分が白金、パラジウム、ルテニウム、ロジウム、イリジウム、ニッケル、コバルト、レニウム、バナジウム、タングステン、モリブデンからなる群から選ばれる少なくとも１種を含有するものが用いられており、触媒担体として表面積９７０ｍ２／ｇのシルカアルミナ系メゾ細孔多孔質材や表面積３２００ｍ２／ｇのアルカリ処理の活性炭が用いられているが、触媒担体の熱伝導性やガス・液の拡散性において重要なシート化については言及されるには至っていなかった。
【０００６】
【発明が解決しようとする課題】
本発明は、かかる事情に鑑み、触媒による水素化反応および脱水素化反応の反応効率の向上を図るために、比表面積が大きく、熱伝導性に優れかつ水素ガス、原料および生成物の拡散性に優れた活性炭担体、該活性炭担体が金属触媒を担持した触媒担持活性炭およびそれらの製造方法を提供することを目的とする。
【０００７】
【課題を解決するための手段】
本発明は、繊維状活性炭からなる活性炭担体であって、Ｘ線光電子分光法（ＸＰＳ）による該活性炭担体上表面のＯ／Ｃ比が１０％以上であり、かつ通気性が２００ｃｍ３／ｃｍ２・ｓ以上であることを特徴とする。
【０００８】
活性炭担体は、繊維状高分子を製編後、炭化して得られ、かつ編物であることが好ましい。さらに、トルエン吸着性能が２５ｇ／ｍ２以上であることが好ましい。
【０００９】
好ましくは、ＢＥＴ法による比表面積が８００〜３０００ｍ２／ｇであり、繊維状活性炭の原料となる繊維状高分子の糸状の繊度が１５０ｄｔｅｘ以上の太さを有してもよい。
【００１０】
別の局面では、本発明の活性炭担体の製造方法は、繊維状高分子を製編して繊維状高分子編物を製造する工程と、該繊維状高分子編物を炭化して繊維状活性炭編物を製造する工程とを包含し、該活性炭担体は、Ｘ線光電子分光法によるＯ／Ｃ比が１０％以上であり、通気性が２００ｃｍ３／ｃｍ２・ｓ以上であることを特徴とする。
【００１１】
また、本発明は、上記の活性炭担体に金属触媒が担持した触媒担持活性炭を提供し、該触媒担持活性炭は、好ましくは、トルエン吸着性能が、１５ｇ／ｍ２以上であり、ＢＥＴ法により求めた比表面積が、５００〜２４００ｍ２／ｇである。
【００１２】
また別の局面では、本発明の触媒担持活性炭の製造方法は、繊維状高分子を製編して繊維状高分子編物を製造する工程と、該繊維状高分子編物を炭化して繊維状活性炭編物を製造する工程と、表面処理後の繊維状活性炭編物に金属触媒を担持させる工程と、を包含し、該触媒担持活性炭は通気性が２００ｃｍ３／ｃｍ２・ｓ以上であることを特徴とする。
【００１３】
【発明の実施の形態】
本発明にかかる活性炭担体は、比表面積を大きくするために、繊維状活性炭により構成されることを必要とする。本発明にかかる活性炭担体は、繊維状であれば特に形状は問わないが、繊維状活性炭は編物であることが、活性炭担体の通気性を向上させる観点から、好ましい形態である。また、単繊維でなく繊維束とすることにより熱伝導率が良くなり、また疎な組織であるため通気性の向上が可能になる。
【００１４】
繊維状活性炭編物の製造方法について特に制限はないが、繊維状高分子を製編後、炭化処理および必要に応じて賦活処理する方法が好ましい方法として挙げられる。そして、表面処理をさらに行なうことにより、触媒を効率良く担持することができ、またトルエンなどの吸着能も向上し、水素化および脱水素化反応の良好な触媒担体として使用することができる。
【００１５】
本発明において、繊維状活性炭の原料となる繊維状高分子の材質は、フェノール系繊維であることが望ましい。繊維状活性炭の原料繊維としては他にセルロース系、ピッチ系やＰＡＮ系などがある。セルロース系繊維を原料繊維とする場合は、炭化・賦活により十分な吸着性能を発揮する比表面積を有する繊維状活性炭が得られるが、収率が低く、また収縮率が大きいので剛性が高く、布帛の強度、特に引裂強さの小さいものとなる。ＰＡＮ系繊維を原料繊維とする場合は、比較的布帛強度の高いものが得られるが、大きな吸着性能を有する繊維状活性炭を得ることが困難である。ピッチ系繊維を用いるとセルロース系とＰＡＮ系の中間程度の強度と吸着性能が得られるが、必ずしも両方の特性とも満足するものではない。
【００１６】
本発明において、繊維状高分子の形状は、ステープルから得られる紡績糸あるいはフィラメント糸のいずれの場合でもよく、また両者を混合した混繊糸状でもよい。全体としての糸状の繊度は、１５０ｄｔｅｘ以上、好ましくは２９５〜５９０ｄｔｅｘがよい。１５０ｄｔｅｘ以下の場合、製編し、炭化および賦活した後の繊維状活性炭編物の密度が緻密となって十分な通気性が得られないからである。
【００１７】
紡績糸または混繊糸の場合、それを構成する各単繊維の繊度は、１．１ｄｔｅｘ〜５．５ｄｔｅｘがよい。単繊維繊度が１．１ｄｔｅｘ以下であると、加工後の単繊維強度が著しく弱くなり、編物を保持することができず、また単繊維繊度が５．５ｄｔｅｘ以上であると、炭化、賦活の進行具合が繊維表面と内部で偏りを生じ、単繊維強度が著しく弱くなり、編物を保持することができないからである。
【００１８】
このような糸状を用いて原料編地を製編するにあたって、繊維状活性炭にした後の編地の通気性と熱伝導性を保持するためには編組織としてはリブ編または両面編が好ましい。この中でもフライス網やスムース編は連続焼成する際に生地の収縮によるコース方向の応力によって生じる生地の耳部の巻き込みがほとんどなく、繊維状活性炭編物の均一な形態保持の点で好ましい。
【００１９】
このようにして得られた原料編地を活性炭にする際には、炭化処理、必要に応じて賦活処理を行なうことができ、炭化および賦活処理を行なう場合は、バッチ式あるいは連続式に炭化および賦活することにより得ることができる。繊維状活性炭編物の生地特性や吸着性能の均一性を得ることや工業的生産性を考慮すると、炭化および賦活を連続的に行なうことが好ましい。原料シートを３５０℃以上１３００℃以下の温度の不活性雰囲気で炭化し、次いで５００℃以上１３００℃以下の温度で炭素と反応する水蒸気、酸素、二酸化炭素などを含む活性な雰囲気で賦活し活性炭化する。
【００２０】
また、場合によっては雰囲気条件を制御することにより炭化と賦活を同時に行なうことも可能である。なお、賦活処理、すなわち活性炭化を行なう際の最高到達温度を１３００℃を超えると重量収率が著しく減少するため、最高到達温度は１３００℃以下にすることが好ましい。これにより、ＢＥＴ法による比表面積が５００〜３０００ｍ２／ｇである繊維状活性炭が得られる。
【００２１】
また、本発明にかかる活性炭担体は、ＸＰＳによるＯ／Ｃ比が、１０％以上であることを必要とする。Ｏ／Ｃ比が、１０％未満であると、水溶液系で触媒を担持する際の濡れ性が悪く均一に担持できず、また脱水素反応における反応原料および生成物の拡散性が著しく低下し、反応効率を低下させるからである。ここで、Ｏ／Ｃ比における、「Ｏ」および「Ｃ」は、それぞれ酸素原子および炭素原子を表わす。
【００２２】
したがって、本発明の活性炭担体は、ＸＰＳによるＯ／Ｃ比が１０％未満である場合には、１０％以上になるように酸素雰囲気中で表面処理を行なう。これにより、繊維状活性炭の表面に酸素含有官能基を導入することができる。ここで、酸素含有官能基は、カルボキシル基、水酸基、ケトン基、ラクトン基などが挙げられるが、これらに限定されない。表面処理の方法は特に限定されないが、たとえば、１．３３Ｐａ以上の酸素分圧を有する酸素雰囲気下で、３００〜７００℃の温度にて、重量収率にして６５〜９９％の範囲にように乾式酸化することが好ましい。低温では処理する炭素材料の反応性が落ちるため、酸化の効果が得られない。また高温では表面に水酸基やカルボキシル基などの親水基が付与できない場合がある。特に、酸性基を強固に固定するためには４５０〜７００℃で行なうことや、ホウ素、窒素などを導入するような炭化・賦活をすることが望ましい。酸素雰囲気中であれば強酸や電気酸化などによる湿式処理、プラズマ処理でも同様な効果を得ることができる。これにより、Ｏ／Ｃ比が１０〜４０％である編物状の繊維状活性炭を得ることが好ましい。より好ましくはＯ／Ｃ比が１５〜４０％であり、さらに好ましくは２０〜４０％である。
【００２３】
本発明において、表面処理された後の活性炭担体の目付量は、５０〜３００ｇ／ｍ２が好ましい。５０ｇ／ｍ２以下の場合は、活性炭の強度が弱く、３００ｇ／ｍ２以上の場合は、通気性が悪くなるからである。より好ましくは、６０〜１５０ｇ／ｍ２である。
【００２４】
また、本発明にかかる活性炭担体は、通気性（編物状の活性炭担体である場合は、厚み方向の通気性）が２００ｃｍ３／ｃｍ２・ｓ以上であることを必要とする。通気性が２００ｃｍ３／ｃｍ２・ｓ未満であれば、触媒担体として用いた場合、生成した水素ガスの拡散が悪くなり、反応効率が低下するからである。
【００２５】
また、活性炭担体のトルエン吸着性能またはＢＥＴ法による比表面積等の吸着性能も触媒を担持する際の重要な指標となる。つまり、トルエン吸着性能とＢＥＴ法による比表面積はいずれも触媒の担持、脱水素反応場としてのスペースを評価する点で共通するため相当の相関が認められるが、トルエン吸着性能は脱水素化反応における原料、生成物類似の化合物であるトルエンを用いて、主として反応場を評価するのに対し、ＢＥＴ法による比表面積は、窒素ガスを用いて、主として触媒の担持場を評価する点で異なり、それぞれ重要な指標である。
【００２６】
本発明にかかる活性炭担体は、トルエン吸着性能が２５ｇ／ｍ２以上であることが好ましい。２５ｇ／ｍ２未満の場合は、脱水素および水素化反応に使用する原料化合物の反応場の低減より、触媒担持活性炭の性能が低下するからである。また、ＢＥＴ法による比表面積は、８００ｍ２／ｇ〜３０００ｍ２／ｇであることが好ましい。８００ｍ２／ｇ未満であると触媒の担持量が低下し触媒担持活性炭の性能が低下し、３０００ｍ２／ｇを超えると繊維の比重が著しく低下し担体の強度が低下するからである。
【００２７】
本発明において、触媒担持活性炭とは、前記活性炭担体に金属触媒を担持させたものをいい、脱水素化または水素化反応等の触媒として使用し得る。本発明にかかる触媒担持活性炭は、上記活性炭担体に担持させたものであるので、比表面積が増大しており、水素ガス、反応原料および生成物の拡散性が向上しており、反応効率も高く、非常に高性能である。
【００２８】
上記金属触媒としては、白金、パラジウム、ルテニウム、ロジウム、イリジウム、ニッケル、コバルト、レニウム、バナジウム、タングステン、モリブデン等の各種触媒が挙げられるが、これらに限定されない。また、これらの触媒を複数組合せて用いることもできる。活性炭担体に触媒を担持させる方法は、特に限定されないが、たとえば、白金を担持させる場合、１０質量％以下の塩化白金酸水溶液に該活性炭担体を１２時間以上浸漬し、乾燥することによって行なうことができる。また、溶液はメタノール、エタノール、アセトン等の水溶性有機溶媒で希釈した水溶液を用いることもできる。なお、触媒活性を高めるため、使用前に還元処理を行なうことが極めて好ましい。
【００２９】
本発明にかかる触媒担持活性炭は、トルエン吸着性能が１５ｇ／ｍ２以上であり、ＢＥＴ法による比表面積が５００〜２４００ｍ２／ｇであることが好ましい。トルエン吸着性能が１５ｇ／ｍ２未満であり、比表面積が５００ｍ２／ｇ未満であると、十分な触媒活性が得られず、比表面積が２４００ｍ２／ｇを超えると、触媒担持活性炭を構成する繊維状活性炭の比重が低下し触媒担持活性炭の機械的強度が低下するからである。
【００３０】
また、本発明にかかる触媒担持活性炭においては、通気性が触媒を担持する前の通気性と同様であることが好ましい。すなわち、触媒を担持した後の通気性も、２００ｃｍ３／ｃｍ２・ｓ以上であることが好ましい。触媒を担持した後の通気性が２００ｃｍ３／ｃｍ２・ｓ未満の場合は、脱水素反応において生成した水素ガスの拡散が悪くなり、反応効率が低下するからである。
【００３１】
【実施例】
以下、実施例を挙げて本発明をより詳細に説明するが、本発明はこれらに限定されるものではない。なお、繊維状高分子編物、繊維状活性炭編物、活性炭担体および触媒担持活性炭についての各特性値の測定方法は以下のとおりである。
【００３２】
（１）通気性
通気性は、ＪＩＳ Ｌ１０１８に準拠して、圧力１２５ｈＰａにて単位面積当たりに試料を通過する空気の速度（ｃｍ３／ｃｍ２・ｓ）を測定した。
【００３３】
（２）トルエン吸着性能
トルエン吸着性能は、ＪＩＳ １４７７に準拠して、２５℃で乾燥空気で１／１０に希釈したトルエン蒸気を通じたときの、試料単位面積当たりに吸着したトルエン質量（ｇ／ｍ２）を測定した。
【００３４】
（３）比表面積
比表面積は、液体窒素の沸点（−１９５．８℃）雰囲気下、相対圧力０．０〜０．２の範囲で上昇させたときの試料への窒素吸着量を数点測定し、ＢＥＴプロットにより試料単位質量当たりの表面積（ｍ２／ｇ）を求めた。なお、試料は、予め１Ｍの塩酸水溶液で１２時間洗浄し、十分に水荒いし乾燥したものを、約０．１ｇ採取し１２０℃で１２時間真空乾燥させたものを使用した。
【００３５】
（４）ＸＰＳによるＯ／Ｃ比の測定
Ｘ線光電子分光法（ＥＳＣＡまたはＸＰＳと称される）による測定に用いた装置は島津ＥＳＣＡ７５０で、解析には島津ＥＳＣＡＰＡＣ７６０を使用した。Ｏ／Ｃ比は、以下の手順により求めた。予め、測定前に試料を１２０℃に加熱し、３時間以上真空脱気した。試料を６ｍｍ径に打ち抜き、導電性ペーストにより加熱式試料台に貼り付け、分析に供した。線源にはＭｇＫα線（１２５３．６ｅＶ）を用い、装置内真空度は１３３×１０−７Ｐａとした。測定はＣ１ｓピーク、Ｏ１ｓピークに対して行ない、各ピーク面積を求めた。得られた面積は、Ｃ１ｓピークについては１．００、Ｏ１ｓピークについては２．８５の相対強度を乗じたものであり、その面積から直接表面（酸素／炭素）原子数比を百分率（％）で算出した。
【００３６】
（５）水素発生速度
図１に水素発生装置の概略図を示す。１０ｃｍ２（直径３．５ｃｍ）の触媒担持活性炭２をアルゴン置換された丸底フラスコ１の下部に設置し、丸底フラスコ１の下方に設けた電気ヒータ３により２００℃に熱しながら、該触媒担持活性炭に噴霧器付き水素化物導入部９よりシクロヘキサンを１０ｍｌ／分にて吹き付けた。生成した水素ガスは冷却管４を通って水素捕集管６に捕集され、生成したベンゼンは未反応のシクロヘキサンとともに冷却管７を通って芳香族回収部８に回収された。３０分後と５時間後の水素ガスの発生速度（Ｌ／ｍｉｎ）を測定した。
【００３７】
（実施例１）
単繊維繊度２．２ｄｔｅｘ、糸状の繊度２９５ｄｔｅｘのフェノール系繊維を使用し、２２ゲージ両面丸編み機によりフライス編物を編成した。この編物は、目付２２５ｇ／ｍ２、厚さ１．６５ｍｍ、見掛密度０．１４ｇ／ｃｍ３、通気性は３３０ｃｍ３／ｃｍ２・ｓであった。
【００３８】
この編物を常温から８９０℃まで３０分間、不活性雰囲気中で炭化させ、次に水蒸気１２質量％を含有する雰囲気中８９０℃の温度で９０分間賦活した。得られた編物状の繊維状活性炭編物は、絶乾目付１２０ｇ／ｍ２、厚さ１．０５ｍｍ、通気性は３３０ｃｍ３／ｃｍ２・ｓであった。また、この繊維状活性炭編物のトルエン吸着性能は５４ｇ／ｍ２、ＢＥＴ比表面積は１３８０ｍ２／ｇと非常に高い吸着性能を有するものであった。
【００３９】
この編物状の繊維状活性炭編物をさらに空気中４５０℃で５分間熱処理を行った。重量収率は９７質量％であり、絶乾目付１１６ｇ／ｍ２、厚さ１．０５ｍｍ、通気性３３０ｃｍ３／ｃｍ２・ｓ、ＸＰＳによるＯ／Ｃ比は１２であった。また、トルエン吸着性能は５２ｇ／ｍ２、ＢＥＴ比表面積は、１３８０ｍ２／ｇと高い吸着性能を示した。
【００４０】
さらに、塩化白金酸の水溶液に該編物状の繊維状活性炭編物を浸漬し、５質量％の白金触媒担持活性炭を調製した。この白金触媒担持活性炭のトルエン吸着性能は４２ｇ／ｍ２、ＢＥＴ比表面積は１１００ｍ２／ｇ、通気性は３３０ｃｍ３／ｃｍ２・ｓ、であった。この白金触媒担持活性炭１０ｃｍ２を１２０℃で１２時間真空乾燥して還元した後、水素ガスの発生速度（Ｌ／ｍｉｎ）を測定したところ、３０分後の水素発生速度は５．１Ｌ／ｍｉｎで、５時間後も５．０Ｌ／ｍｉｎと非常に良好であった。結果を表１に示す。
【００４１】
（実施例２）
実施例１と同じフライス編地を編成し、同じ条件で炭化および賦活処理した。得られた編物状の繊維状活性炭編物は、実施例１と同じ物性を有していた。この編物状の繊維状活性炭編物をさらに空気中４５０℃で１０分間熱処理を行った。重量収率は９３質量％であり、絶乾目付１１２ｇ／ｍ２、厚さ１．０５ｍｍ、通気性３３０ｃｍ３／ｃｍ２・ｓ、ＸＰＳによるＯ／Ｃ比は３０であった。また、トルエン吸着性能は５０ｇ／ｍ２、ＢＥＴ比表面積は、１３８０ｍ２／ｇであった。
【００４２】
さらに、実施例１と同様に、５質量％の白金触媒担持活性炭を調製した。この白金触媒担持活性炭のトルエン吸着性能は４１ｇ／ｍ２、ＢＥＴ比表面積は１１５０ｍ２／ｇ、通気性は３３０ｃｍ３／ｃｍ２・ｓ、であった。この白金触媒担持活性炭１０ｃｍ２を１２０℃で１２時間真空乾燥して還元した後、水素ガスの発生速度（Ｌ／ｍｉｎ）を測定したところ、３０分後の水素発生速度は５．５Ｌ／ｍｉｎで、５時間後も５．５Ｌ／ｍｉｎと非常に良好であった。結果を表１に示す。
【００４３】
（実施例３）
実施例１と同じフライス編地を編成し、同じ条件で炭化および賦活処理した。得られた編物状の繊維状活性炭編物は、実施例１と同じ物性を有していた。この編物状の繊維状活性炭編物をさらに空気中４５０℃で１５分間熱処理を行った。重量収率は９０質量％であり、絶乾目付１０８ｇ／ｍ２、厚さ１．０５ｍｍ、通気性３３０ｃｍ３／ｃｍ２・ｓ、ＸＰＳによるＯ／Ｃ比は４３であった。また、トルエン吸着性能は５０ｇ／ｍ２、ＢＥＴ比表面積は、１３６０ｍ２／ｇであった。
【００４４】
さらに、実施例１と同様に、５質量％の白金触媒担持活性炭を調製した。この白金触媒担持活性炭のトルエン吸着性能は４１ｇ／ｍ２、ＢＥＴ比表面積は１１８０ｍ２／ｇ、通気性は３３０ｃｍ３／ｃｍ２・ｓ、であった。この白金触媒担持活性炭１０ｃｍ２を１２０℃で１２時間真空乾燥して還元した後、水素ガスの発生速度（Ｌ／ｍｉｎ）を測定したところ、３０分後の水素発生速度は５．２Ｌ／ｍｉｎで、５時間後も５．２Ｌ／ｍｉｎと非常に良好であった。結果を表１に示す。
【００４５】
（実施例４）
実施例１と同じフライス編地を編成し、この編物を常温から８９０℃まで３０分間、不活性雰囲気中で炭化させ、次に水蒸気１２質量％を含有する雰囲気中８９０℃の温度で７０分間賦活した。得られた編物状の繊維状活性炭編物は、絶乾目付１２６ｇ／ｍ２、厚さ１．１０ｍｍ、通気性は３３０ｃｍ３／ｃｍ２・ｓであった。また、この繊維状活性炭編物のトルエン吸着性能は５０ｇ／ｍ２、ＢＥＴ比表面積は１２５０ｍ２／ｇと非常に高い吸着性能を有するものであった。
【００４６】
この編物状の繊維状活性炭編物をさらに空気中４５０℃で１０分間熱処理を行った。重量収率は９５質量％であり、絶乾目付１２０ｇ／ｍ２、厚さ１．１０ｍｍ、通気性３３０ｃｍ３／ｃｍ２・ｓ、ＸＰＳによるＯ／Ｃ比は４０であった。また、トルエン吸着性能は４８ｇ／ｍ２、ＢＥＴ比表面積は、１２５０ｍ２／ｇであった。
【００４７】
さらに、実施例１と同様に、５質量％の白金触媒担持活性炭を調製した。この白金触媒担持活性炭のトルエン吸着性能は４２ｇ／ｍ２、ＢＥＴ比表面積は１０７０ｍ２／ｇ、通気性は３３０ｃｍ３／ｃｍ２・ｓ、であった。この白金触媒担持活性炭１０ｃｍ２を１２０℃で１２時間真空乾燥して還元した後、水素ガスの発生速度（Ｌ／ｍｉｎ）を測定したところ、３０分後の水素発生速度は４．８Ｌ／ｍｉｎで、５時間後も４．７Ｌ／ｍｉｎと非常に良好であった。結果を表１に示す。
【００４８】
（比較例１）
実施例１と同じフライス編地を編成し、同じ条件で炭化および賦活処理した。得られた編物状の繊維状活性炭編物は、実施例１と同様に、絶乾目付１２０ｇ／ｍ２、厚さ１．０５ｍｍ、通気性は３３０ｃｍ３／ｃｍ２・ｓであった。また、この繊維状活性炭編物のトルエン吸着性能は５４ｇ／ｍ２、ＢＥＴ比表面積は１３８０ｍ２／ｇと非常に高い吸着性能を有するものであった。この編物状の繊維状活性炭編物を空気中での熱処理を行なわず、実施例１と同様に、５質量％の白金触媒担持活性炭を調製した。この白金触媒担持活性炭のトルエン吸着性能は３４ｇ／ｍ２、ＢＥＴ比表面積は８４０ｍ２／ｇ、通気性は３３０ｃｍ３／ｃｍ２・ｓ、であった。この白金触媒担持活性炭１０ｃｍ２を１２０℃で１２時間真空乾燥して還元した後、水素ガスの発生速度（Ｌ／ｍｉｎ）を測定したところ、３０分後の水素発生速度は３．３Ｌ／ｍｉｎで、５時間後は３．２Ｌ／ｍｉｎであった。結果を表１に示す。
【００４９】
（比較例２）
実施例１と同じフライス編地を編成し、この編物を常温から８９０℃まで２０分間、不活性雰囲気中で炭化させ、次に水蒸気１２質量％を含有する雰囲気中８９０℃の温度で２０分間賦活した。得られた編物状の繊維状活性炭編物は、絶乾目付１３０ｇ／ｍ２、厚さ１．１０ｍｍ、通気性は３３０ｃｍ３／ｃｍ２・ｓであった。また、この繊維状活性炭編物のトルエン吸着性能は４３ｇ／ｍ２、ＢＥＴ比表面積は１０１０ｍ２／ｇと非常に高い吸着性能を有するものであった。
【００５０】
この編物状の繊維状活性炭編物を空気中での熱処理を行なわず、実施例１と同様に、５質量％の白金触媒担持活性炭を調製した。この白金触媒担持活性炭のトルエン吸着性能は２９ｇ／ｍ２、ＢＥＴ比表面積は７１０ｍ２／ｇ、通気性は３３０ｃｍ３／ｃｍ２・ｓ、であった。この白金触媒担持活性炭１０ｃｍ２を１２０℃で１２時間真空乾燥して還元した後、水素ガスの発生速度（Ｌ／ｍｉｎ）を測定したところ、３０分後の水素発生速度は３．２Ｌ／ｍｉｎで、５時間後は３．１Ｌ／ｍｉｎであった。結果を表１に示す。
【００５１】
（比較例３）
単繊維繊度２．２ｄｔｅｘ、糸状の繊度２９５ｄｔｅｘのフェノール系繊維を使用し、１８ゲージ両面丸編み機によりスムース編物を編成した。この編物は、目付１４０ｇ／ｍ２、厚さ１．１０ｍｍ、見掛密度０．１４ｇ／ｃｍ３、通気性は１７４ｃｍ３／ｃｍ２・ｓであった。
【００５２】
この編物を実施例１と同様に、常温から８９０℃まで３０分間、不活性雰囲気中で炭化させ、次に水蒸気１２質量％を含有する雰囲気中８９０℃の温度で９０分間賦活した。得られた編物状の繊維状活性炭編物は、絶乾目付１４０ｇ／ｍ２、厚さ１．１０ｍｍ、通気性は１７４ｃｍ３／ｃｍ２・ｓであった。また、この繊維状活性炭編物のトルエン吸着性能は６０ｇ／ｍ２、ＢＥＴ比表面積は１３３０ｍ２／ｇであった。
【００５３】
この編物状の繊維状活性炭編物を実施例２と同様に、さらに空気中４５０℃で１０分間熱処理を行った。重量収率は９３質量％であり、絶乾目付１３０ｇ／ｍ２、厚さ１．１０ｍｍ、ＸＰＳによるＯ／Ｃ比は２５であった。また、トルエン吸着能性能は５６ｇ／ｍ２、ＢＥＴ比表面積は、１３３０ｍ２／ｇ、通気性は１７４ｃｍ３／ｃｍ２・ｓであった。
【００５４】
さらに、実施例１と同様に、５質量％の白金触媒担持活性炭を調製した。この白金触媒担持活性炭のトルエン吸着性能は４３ｇ／ｍ２、ＢＥＴ比表面積は９９０ｍ２／ｇ、通気性は１７４ｃｍ３／ｃｍ２・ｓであった。この白金触媒担持活性炭１０ｃｍ２を１２０℃で１２時間真空乾燥して還元した後、水素ガスの発生速度（Ｌ／ｍｉｎ）を測定したところ、３０分後の水素発生速度は２．２Ｌ／ｍｉｎで、５時間後は２．０Ｌ／ｍｉｎであった。結果を表１に示す。
【００５５】
【表１】
表１において、触媒担持前の数値は、繊維状活性炭に表面処理を行なった後の数値を表すが、比較例１および２においては、表面処理を行なっていないので、炭化および賦活後の数値を表わす。
【００５７】
上記結果より、実施例１〜４の触媒担持活性炭は、表面処理を行なってＯ／Ｃ比が１０％以上であるので、水素ガス発生量も多く、脱水素反応などの良好な触媒として使用することができる。一方、比較例１および２の触媒担持活性炭は、表面処理を行なっていなく、Ｏ／Ｃ比が１０％未満であるので、水素ガス発生量が低い。
【００５８】
また、実施例２と比較例３とを対比させると、実施例２は、比較例３に比べて水素発生量が明らかに多いことがわかる。したがって、繊維状高分子の編み方は、スムース編よりもフライス編みが好ましいことがわかる。なぜなら、フライス編は、スムース編と比べて良好な通気性を達成することができるからである。
【００５９】
今回開示された実施の形態および実施例はすべての点で例示であって制限的なものではないと考えられるべきである。本発明の範囲は上記した説明ではなくて特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内でのすべての変更が含まれることが意図される。
【００６０】
【発明の効果】
上述のとおり、本発明の活性炭担体および触媒担持活性炭は、繊維状構造、特に、編物構造をとっているため通気性が高いので、熱伝導性に優れ、水素ガス、水素化または脱水素化反応における反応原料および生成物の拡散性に優れている。また、本発明にかかる活性炭担体は、Ｏ／Ｃ比が１０％以上であるので、触媒を担持する能力が飛躍的に向上し、反応原料および生成物も良好に拡散することができる。このため、本発明の触媒担持活性炭は、水素化および脱水素化反応の反応効率を向上することができ、高性能の触媒担体または触媒として機能し得る。
【図面の簡単な説明】
【図１】本発明に用いられる水素発生装置の概略図である。
【符号の説明】
１ 丸底フラスコ、２ 触媒担持活性炭、３ 電気ヒータ、４ 冷却管、５ コック、６ 水素捕集管、７ 冷却管、８ 芳香族回収部、９ 噴霧器付き水素化物導入部。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a fibrous activated carbon for supporting a metal catalyst and a fibrous activated carbon supporting a metal catalyst, and more particularly to an electrode of a solid polymer electrolyte fuel cell, which is used for hydrogenation and dehydrogenation reactions. The present invention relates to an activated carbon carrier and a catalyst-supporting activated carbon used.
[0002]
For example, a system for hydrogenating a monocyclic aromatic compound such as benzene, toluene, xylene, and mesitylene, a bicyclic aromatic compound such as naphthalene and methylnaphthalene, and a tricyclic aromatic compound such as anthracene, or a hydride cyclohexane; Monocyclic hydrogenated aromatic compounds such as methylcyclohexane and dimethylcyclohexane; bicyclic hydrogenated aromatic compounds such as tetralin, decalin and methyldecalin; and tricyclic hydrogenated aromatic compounds such as tetradecahydroanthracene and tetradecahydromethylanthracene The present invention relates to an activated carbon carrier and a catalyst-supporting activated carbon used in a system for dehydrogenating a compound.
[0003]
[Prior art]
Conventionally, as a carrier for supporting a catalyst, granular activated carbon having a large surface area and high chemical resistance, activated carbon paper, and the like have been used. For example, a catalyst carrier used in a system for dehydrogenating hydride requires an atmosphere of up to 400 ° C. in order to promote the reaction because the dehydrogenation reaction is an endothermic reaction, and therefore has excellent thermal conductivity, and It is required to have excellent diffusivity for products such as hydrogen gas and aromatic compounds, but sufficient performance has not been obtained.
[0004]
For example, Japanese Patent Application Laid-Open No. 2001-110439 has devised a system in which hydrogen is generated and separated by a dehydrogenation catalytic reactor heated from a hydrogenated aromatic compound raw material at room temperature and supplied to a fuel cell. This system has a feature that high-purity hydrogen can be efficiently produced and supplied without generating by-products such as CO and CO 2 , and the system can be made compact.
[0005]
In the above publication, a catalyst containing an active component containing at least one selected from the group consisting of platinum, palladium, ruthenium, rhodium, iridium, nickel, cobalt, rhenium, vanadium, tungsten and molybdenum is used as a catalyst. As the material, a silica silicate mesoporous porous material having a surface area of 970 m 2 / g or an activated carbon treated with an alkali having a surface area of 3200 m 2 / g is important in terms of the thermal conductivity of the catalyst carrier and the diffusibility of gas and liquid. No mention was made of sheeting.
[0006]
[Problems to be solved by the invention]
In view of such circumstances, the present invention has a large specific surface area, excellent thermal conductivity, and excellent diffusivity of hydrogen gas, raw materials and products in order to improve the reaction efficiency of hydrogenation and dehydrogenation reactions using a catalyst. It is an object of the present invention to provide an activated carbon carrier excellent in the above, a catalyst-supported activated carbon in which the activated carbon carrier carries a metal catalyst, and a method for producing the same.
[0007]
[Means for Solving the Problems]
The present invention relates to an activated carbon carrier comprising fibrous activated carbon, wherein the O / C ratio of the surface of the activated carbon carrier by X-ray photoelectron spectroscopy (XPS) is 10% or more, and air permeability is 200 cm 3 / cm 2. -It is characterized by being s or more.
[0008]
The activated carbon carrier is obtained by knitting and knitting a fibrous polymer, and is preferably a knit. Further, the toluene adsorption performance is preferably 25 g / m 2 or more.
[0009]
Preferably, the specific surface area according to the BET method is from 800 to 3000 m 2 / g, and the fibrous size of the fibrous polymer used as the raw material of the fibrous activated carbon may be 150 dtex or more.
[0010]
In another aspect, the method for producing an activated carbon carrier of the present invention comprises the steps of: knitting a fibrous polymer to produce a fibrous polymer knit; and carbonizing the fibrous polymer knit to form a fibrous activated carbon knit. The activated carbon carrier is characterized in that the activated carbon support has an O / C ratio by X-ray photoelectron spectroscopy of 10% or more and a gas permeability of 200 cm 3 / cm 2 · s or more.
[0011]
Further, the present invention provides a catalyst-supported activated carbon in which a metal catalyst is supported on the above-mentioned activated carbon carrier, and the catalyst-supported activated carbon preferably has a toluene adsorption performance of 15 g / m 2 or more, and was determined by a BET method. The specific surface area is 500 to 2400 m 2 / g.
[0012]
In another aspect, the method for producing a catalyst-supporting activated carbon of the present invention comprises the steps of knitting a fibrous polymer to produce a fibrous polymer knit, and carbonizing the fibrous polymer knit to produce a fibrous activated carbon. The method includes a step of producing a knitted article and a step of supporting a metal catalyst on the fibrous activated carbon knitted article after surface treatment, wherein the catalyst-carrying activated carbon has a gas permeability of 200 cm 3 / cm 2 · s or more. I do.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
The activated carbon carrier according to the present invention needs to be constituted by fibrous activated carbon in order to increase the specific surface area. The shape of the activated carbon carrier according to the present invention is not particularly limited as long as it is fibrous. However, the fibrous activated carbon is preferably a knitted fabric from the viewpoint of improving the gas permeability of the activated carbon carrier. Further, by using a fiber bundle instead of a single fiber, the thermal conductivity is improved, and the air permeability can be improved due to the sparse structure.
[0014]
The method for producing the fibrous activated carbon knit is not particularly limited, but a method in which the fibrous polymer is knitted, then carbonized and, if necessary, activated is mentioned as a preferred method. Further, by further performing the surface treatment, the catalyst can be efficiently supported, the adsorption ability of toluene and the like can be improved, and the catalyst can be used as a favorable catalyst carrier for hydrogenation and dehydrogenation reactions.
[0015]
In the present invention, the material of the fibrous polymer serving as the raw material of the fibrous activated carbon is desirably phenolic fibers. Other examples of the raw material fiber of the fibrous activated carbon include a cellulose type, a pitch type, and a PAN type. When a cellulosic fiber is used as a raw material fiber, a fibrous activated carbon having a specific surface area capable of exhibiting sufficient adsorption performance by carbonization and activation can be obtained. , Particularly low tear strength. When a PAN fiber is used as a raw material fiber, a fiber having a relatively high fabric strength can be obtained, but it is difficult to obtain a fibrous activated carbon having a large adsorption performance. When pitch-based fibers are used, an intermediate strength and adsorption performance between cellulose-based and PAN-based fibers can be obtained, but both properties are not necessarily satisfied.
[0016]
In the present invention, the shape of the fibrous polymer may be either a spun yarn or a filament yarn obtained from staples, or may be a mixed fiber obtained by mixing both. The thread-like fineness as a whole is 150 dtex or more, and preferably 295 to 590 dtex. If it is 150 dtex or less, the density of the knitted fibrous activated carbon after knitting, carbonization and activation is so dense that sufficient air permeability cannot be obtained.
[0017]
In the case of a spun yarn or a mixed fiber, the fineness of each of the single fibers constituting the spun yarn or the mixed fiber is preferably from 1.1 dtex to 5.5 dtex. If the single fiber fineness is 1.1 dtex or less, the strength of the single fiber after processing becomes extremely weak, and the knitted fabric cannot be held. If the single fiber fineness is 5.5 dtex or more, carbonization and activation progress. This is because the condition is deviated between the fiber surface and the inside, the strength of the single fiber is significantly reduced, and the knitted fabric cannot be held.
[0018]
In knitting a raw knitted fabric using such a thread shape, a rib knit or double-sided knitting is preferable as a knitting structure in order to maintain the air permeability and the thermal conductivity of the knitted fabric after the fibrous activated carbon is formed. Among them, the milling net or the smooth knitting is preferable in that the ears of the dough are hardly entangled by the stress in the course direction due to the shrinkage of the dough during continuous firing, and the fibrous activated carbon knit is maintained in a uniform shape.
[0019]
When the raw knitted fabric thus obtained is to be activated carbon, carbonization treatment and, if necessary, activation treatment can be carried out. It can be obtained by activating. In view of obtaining uniformity of the fabric properties and adsorption performance of the fibrous activated carbon knitted fabric and considering industrial productivity, it is preferable to continuously perform carbonization and activation. The raw material sheet is carbonized in an inert atmosphere at a temperature of 350 ° C. to 1300 ° C., and then activated in an active atmosphere containing steam, oxygen, carbon dioxide, etc., which reacts with carbon at a temperature of 500 ° C. to 1300 ° C. I do.
[0020]
In some cases, carbonization and activation can be performed simultaneously by controlling the atmospheric conditions. If the maximum temperature during the activation treatment, that is, the activated carbonization, exceeds 1300 ° C., the weight yield is significantly reduced. Therefore, the maximum temperature is preferably 1300 ° C. or lower. Thereby, a fibrous activated carbon having a specific surface area of 500 to 3000 m 2 / g by the BET method is obtained.
[0021]
Further, the activated carbon carrier according to the present invention requires that the O / C ratio by XPS be 10% or more. If the O / C ratio is less than 10%, the wettability when supporting the catalyst in an aqueous solution system is poor and the catalyst cannot be uniformly supported, and the diffusibility of the reaction raw materials and products in the dehydrogenation reaction is significantly reduced, This is because the reaction efficiency is reduced. Here, “O” and “C” in the O / C ratio represent an oxygen atom and a carbon atom, respectively.
[0022]
Therefore, when the O / C ratio by XPS is less than 10%, the activated carbon carrier of the present invention is subjected to a surface treatment in an oxygen atmosphere so as to be 10% or more. Thereby, an oxygen-containing functional group can be introduced into the surface of the fibrous activated carbon. Here, examples of the oxygen-containing functional group include, but are not limited to, a carboxyl group, a hydroxyl group, a ketone group, and a lactone group. The surface treatment method is not particularly limited. For example, under an oxygen atmosphere having an oxygen partial pressure of 1.33 Pa or more, at a temperature of 300 to 700 ° C., a weight yield may be in the range of 65 to 99%. Dry oxidation is preferred. At low temperatures, the reactivity of the carbon material to be treated decreases, so that the effect of oxidation cannot be obtained. At a high temperature, a hydrophilic group such as a hydroxyl group or a carboxyl group may not be provided on the surface in some cases. In particular, in order to firmly fix the acidic group, it is desirable to perform the treatment at 450 to 700 ° C. or to perform carbonization and activation such as introduction of boron, nitrogen, or the like. In an oxygen atmosphere, the same effect can be obtained by a wet treatment using a strong acid or electric oxidation or a plasma treatment. Thereby, it is preferable to obtain a knitted fibrous activated carbon having an O / C ratio of 10 to 40%. More preferably, the O / C ratio is from 15 to 40%, and still more preferably from 20 to 40%.
[0023]
In the present invention, the basis weight of the activated carbon carrier after the surface treatment is preferably from 50 to 300 g / m 2 . If it is 50 g / m 2 or less, the strength of the activated carbon is low, and if it is 300 g / m 2 or more, the air permeability becomes poor. More preferably 60 to 150 g / m 2.
[0024]
Further, the activated carbon carrier according to the present invention needs to have air permeability (in the case of a knitted activated carbon carrier, air permeability in the thickness direction) of 200 cm 3 / cm 2 · s or more. If the gas permeability is less than 200 cm 3 / cm 2 · s, when used as a catalyst carrier, the diffusion of the generated hydrogen gas becomes worse, and the reaction efficiency decreases.
[0025]
In addition, the adsorption performance of the activated carbon carrier such as the toluene adsorption performance or the specific surface area by the BET method is also an important index when the catalyst is supported. In other words, the toluene adsorption performance and the specific surface area by the BET method are both common in that they support the catalyst and evaluate the space as a dehydrogenation reaction field, so that a considerable correlation is recognized. The raw material and the reaction surface are mainly evaluated using toluene, which is a compound similar to the product, whereas the specific surface area by the BET method is different in that the catalyst support site is mainly evaluated using nitrogen gas. It is an important indicator.
[0026]
The activated carbon carrier according to the present invention preferably has a toluene adsorption performance of 25 g / m 2 or more. If the amount is less than 25 g / m 2, the performance of the catalyst-supporting activated carbon is reduced due to a reduction in the reaction field of the raw material compounds used in the dehydrogenation and hydrogenation reactions. In addition, the specific surface area by BET method is preferably 800m 2 / g~
[0027]
In the present invention, the catalyst-supported activated carbon refers to the activated carbon carrier on which a metal catalyst is supported, and can be used as a catalyst for a dehydrogenation or hydrogenation reaction. Since the catalyst-supporting activated carbon according to the present invention is supported on the activated carbon carrier, the specific surface area is increased, the diffusivity of hydrogen gas, reaction raw materials and products is improved, and the reaction efficiency is high. , Very high performance.
[0028]
Examples of the metal catalyst include, but are not limited to, various catalysts such as platinum, palladium, ruthenium, rhodium, iridium, nickel, cobalt, rhenium, vanadium, tungsten, and molybdenum. Further, a plurality of these catalysts can be used in combination. The method for supporting the catalyst on the activated carbon carrier is not particularly limited. For example, in the case of supporting platinum, the method can be carried out by immersing the activated carbon carrier in a 10 mass% or less aqueous chloroplatinic acid solution for 12 hours or more and drying. it can. Further, as the solution, an aqueous solution diluted with a water-soluble organic solvent such as methanol, ethanol, or acetone can be used. In order to enhance the catalytic activity, it is extremely preferable to carry out a reduction treatment before use.
[0029]
The catalyst-supporting activated carbon according to the present invention preferably has a toluene adsorption performance of 15 g / m 2 or more and a specific surface area of 500 to 2400 m 2 / g by a BET method. When the toluene adsorption performance is less than 15 g / m 2 and the specific surface area is less than 500 m 2 / g, sufficient catalytic activity cannot be obtained, and when the specific surface area exceeds 2400 m 2 / g, the catalyst-carrying activated carbon is constituted. This is because the specific gravity of the fibrous activated carbon decreases and the mechanical strength of the catalyst-supporting activated carbon decreases.
[0030]
In the catalyst-supporting activated carbon according to the present invention, it is preferable that the gas permeability is the same as the gas permeability before supporting the catalyst. That is, the gas permeability after supporting the catalyst is also preferably 200 cm 3 / cm 2 · s or more. If the gas permeability after supporting the catalyst is less than 200 cm 3 / cm 2 · s, the diffusion of hydrogen gas generated in the dehydrogenation reaction becomes poor, and the reaction efficiency decreases.
[0031]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In addition, the measuring method of each characteristic value about a fibrous polymer knit, a fibrous activated carbon knit, an activated carbon carrier, and a catalyst-carrying activated carbon is as follows.
[0032]
(1) Air permeability The air permeability was measured by measuring the speed (cm 3 / cm 2 · s) of air passing through a sample per unit area at a pressure of 125 hPa according to JIS L1018.
[0033]
(2) Toluene adsorption performance According to JIS 1477, toluene adsorption performance was measured by the mass of toluene adsorbed per unit area of a sample (g / m 2) when passing toluene vapor diluted 1/10 with dry air at 25 ° C. 2 ) was measured.
[0034]
(3) Specific surface area The specific surface area is obtained by measuring several points of the amount of nitrogen adsorbed on a sample when the relative pressure is increased in a range of 0.0 to 0.2 under an atmosphere of liquid nitrogen boiling point (-195.8 ° C). Then, the surface area per unit mass of the sample (m 2 / g) was determined by a BET plot. The sample used was a sample which was previously washed with a 1 M aqueous hydrochloric acid solution for 12 hours, sufficiently roughened and dried, sampled about 0.1 g, and vacuum-dried at 120 ° C. for 12 hours.
[0035]
(4) Measurement of O / C ratio by XPS The apparatus used for measurement by X-ray photoelectron spectroscopy (referred to as ESCA or XPS) was Shimadzu ESCA750, and Shimadzu ESCAPAC760 was used for analysis. The O / C ratio was determined by the following procedure. Before the measurement, the sample was heated to 120 ° C. and vacuum degassed for 3 hours or more. The sample was punched out to a diameter of 6 mm, affixed to a heated sample stand with a conductive paste, and provided for analysis. MgKα radiation (1253.6 eV) was used as the radiation source, and the degree of vacuum in the apparatus was 133 × 10 −7 Pa. The measurement was performed on the C 1s peak and the O 1s peak, and the respective peak areas were determined. The obtained area is obtained by multiplying the relative intensity of 1.00 for the C 1s peak and 2.85 for the O 1s peak, and the surface (oxygen / carbon) atomic ratio is directly calculated as a percentage (% ).
[0036]
(5) Hydrogen generation rate Fig. 1 shows a schematic diagram of the hydrogen generator. 10 cm 2 (3.5 cm diameter) of activated
[0037]
(Example 1)
Using a phenol-based fiber having a single fiber fineness of 2.2 dtex and a thread-like fineness of 295 dtex, a 22-gauge double-sided circular knitting machine was used to knit a milled knit. This knit had a basis weight of 225 g / m 2 , a thickness of 1.65 mm, an apparent density of 0.14 g / cm 3 , and an air permeability of 330 cm 3 / cm 2 · s.
[0038]
The knit was carbonized from ambient temperature to 890 ° C. for 30 minutes in an inert atmosphere and then activated in an atmosphere containing 12% by weight of steam at a temperature of 890 ° C. for 90 minutes. The obtained knitted fibrous activated carbon knitted fabric had an absolutely dry basis weight of 120 g / m 2 , a thickness of 1.05 mm, and a gas permeability of 330 cm 3 / cm 2 · s. In addition, this fibrous activated carbon knitted fabric had a very high adsorption performance of 54 g / m 2 and a BET specific surface area of 1380 m 2 / g.
[0039]
The knitted fibrous activated carbon knit was further heat-treated at 450 ° C. for 5 minutes in air. The weight yield was 97% by mass, the absolute dry weight was 116 g / m 2 , the thickness was 1.05 mm, the air permeability was 330 cm 3 / cm 2 · s, and the O / C ratio by XPS was 12. In addition, toluene adsorption performance was high at 52 g / m 2 , and BET specific surface area was high at 1380 m 2 / g.
[0040]
Further, the knitted fibrous activated carbon knit was immersed in an aqueous solution of chloroplatinic acid to prepare 5% by mass of a platinum catalyst-carrying activated carbon. The toluene adsorption performance of this platinum catalyst-supported activated carbon was 42 g / m 2 , the BET specific surface area was 1100 m 2 / g, and the gas permeability was 330 cm 3 / cm 2 · s. This platinum catalyst-supported activated carbon 10 cm 2 was reduced by vacuum drying at 120 ° C. for 12 hours, and the hydrogen gas generation rate (L / min) was measured. The hydrogen generation rate after 30 minutes was 5.1 L / min. Even after 5 hours, it was very good at 5.0 L / min. Table 1 shows the results.
[0041]
(Example 2)
The same milling fabric as in Example 1 was knitted, and carbonized and activated under the same conditions. The obtained knitted fibrous activated carbon knit had the same physical properties as in Example 1. The knitted fibrous activated carbon knit was further heat-treated at 450 ° C. for 10 minutes in air. The weight yield was 93% by mass, the absolute dry weight was 112 g / m 2 , the thickness was 1.05 mm, the air permeability was 330 cm 3 / cm 2 · s, and the O / C ratio by XPS was 30. Further, the toluene adsorption performance was 50 g / m 2 , and the BET specific surface area was 1,380 m 2 / g.
[0042]
Further, as in Example 1, 5% by mass of activated carbon carrying a platinum catalyst was prepared. This platinum catalyst-supported activated carbon had a toluene adsorption performance of 41 g / m 2 , a BET specific surface area of 1150 m 2 / g, and a gas permeability of 330 cm 3 / cm 2 · s. This platinum catalyst-supported activated carbon 10 cm 2 was reduced by vacuum drying at 120 ° C. for 12 hours, and the hydrogen gas generation rate (L / min) was measured. The hydrogen generation rate after 30 minutes was 5.5 L / min. Even after 5 hours, it was very good at 5.5 L / min. Table 1 shows the results.
[0043]
(Example 3)
The same milling fabric as in Example 1 was knitted, and carbonized and activated under the same conditions. The obtained knitted fibrous activated carbon knit had the same physical properties as in Example 1. The knitted fibrous activated carbon knit was further subjected to a heat treatment in air at 450 ° C. for 15 minutes. The weight yield was 90% by mass, the absolute dry weight was 108 g / m 2 , the thickness was 1.05 mm, the air permeability was 330 cm 3 / cm 2 · s, and the O / C ratio by XPS was 43. Further, the toluene adsorption performance was 50 g / m 2 , and the BET specific surface area was 1,360 m 2 / g.
[0044]
Further, as in Example 1, 5% by mass of activated carbon carrying a platinum catalyst was prepared. This platinum catalyst-supported activated carbon had a toluene adsorption performance of 41 g / m 2 , a BET specific surface area of 1180 m 2 / g, and a gas permeability of 330 cm 3 / cm 2 · s. This platinum catalyst-supported activated carbon (10 cm 2) was reduced by vacuum drying at 120 ° C. for 12 hours, and the hydrogen gas generation rate (L / min) was measured. The hydrogen generation rate after 30 minutes was 5.2 L / min. After 5 hours, the value was very good at 5.2 L / min. Table 1 shows the results.
[0045]
(Example 4)
The same milling knitted fabric as in Example 1 is knitted and the knit is carbonized from ambient temperature to 890 ° C. for 30 minutes in an inert atmosphere, then activated in an atmosphere containing 12% by weight of steam at a temperature of 890 ° C. for 70 minutes. did. The obtained knitted fibrous activated carbon knitted fabric had an absolutely dry basis weight of 126 g / m 2 , a thickness of 1.10 mm, and a gas permeability of 330 cm 3 / cm 2 · s. Further, the fibrous activated carbon knitted fabric had a very high adsorption performance of 50 g / m 2 and a BET specific surface area of 1250 m 2 / g.
[0046]
The knitted fibrous activated carbon knit was further heat-treated at 450 ° C. for 10 minutes in air. The weight yield was 95% by mass, the absolute dry weight was 120 g / m 2 , the thickness was 1.10 mm, the air permeability was 330 cm 3 / cm 2 · s, and the O / C ratio by XPS was 40. Further, the toluene adsorption performance was 48 g / m 2 , and the BET specific surface area was 1250 m 2 / g.
[0047]
Further, as in Example 1, 5% by mass of activated carbon carrying a platinum catalyst was prepared. This platinum catalyst-supported activated carbon had a toluene adsorption performance of 42 g / m 2 , a BET specific surface area of 1070 m 2 / g, and a gas permeability of 330 cm 3 / cm 2 · s. After reducing the platinum catalyst-supported activated carbon 10 cm 2 by vacuum drying at 120 ° C. for 12 hours and measuring the hydrogen gas generation rate (L / min), the hydrogen generation rate after 30 minutes was 4.8 L / min. Even after 5 hours, the value was very good at 4.7 L / min. Table 1 shows the results.
[0048]
(Comparative Example 1)
The same milling fabric as in Example 1 was knitted, and carbonized and activated under the same conditions. As in Example 1, the obtained knitted fibrous activated carbon knitted article had an absolute dry weight of 120 g / m 2 , a thickness of 1.05 mm, and a gas permeability of 330 cm 3 / cm 2 · s. In addition, this fibrous activated carbon knitted fabric had a very high adsorption performance of 54 g / m 2 and a BET specific surface area of 1380 m 2 / g. This knitted fibrous activated carbon knit was not heat-treated in the air, and a 5% by mass platinum catalyst-supported activated carbon was prepared in the same manner as in Example 1. The toluene adsorption performance of this platinum catalyst-supported activated carbon was 34 g / m 2 , the BET specific surface area was 840 m 2 / g, and the gas permeability was 330 cm 3 / cm 2 · s. This platinum catalyst-supported activated carbon 10 cm 2 was reduced by vacuum drying at 120 ° C. for 12 hours, and the hydrogen gas generation rate (L / min) was measured. The hydrogen generation rate after 30 minutes was 3.3 L / min. After 5 hours, the flow rate was 3.2 L / min. Table 1 shows the results.
[0049]
(Comparative Example 2)
The same milling knitted fabric as in Example 1 is knitted, and the knit is carbonized from room temperature to 890 ° C. for 20 minutes in an inert atmosphere, and then activated in an atmosphere containing 12% by mass of steam at a temperature of 890 ° C. for 20 minutes. did. The obtained knitted fibrous activated carbon knitted fabric had an absolutely dry basis of 130 g / m 2 , a thickness of 1.10 mm, and an air permeability of 330 cm 3 / cm 2 · s. Further, the fibrous activated carbon knitted fabric had a very high adsorption performance of 43 g / m 2 and a BET specific surface area of 1010 m 2 / g.
[0050]
This knitted fibrous activated carbon knit was not heat-treated in the air, and a 5% by mass platinum catalyst-supported activated carbon was prepared in the same manner as in Example 1. This platinum catalyst-supported activated carbon had a toluene adsorption performance of 29 g / m 2 , a BET specific surface area of 710 m 2 / g, and a gas permeability of 330 cm 3 / cm 2 · s. The platinum catalyst-supported activated carbon 10 cm 2 was reduced by vacuum drying at 120 ° C. for 12 hours, and the hydrogen gas generation rate (L / min) was measured. The hydrogen generation rate after 30 minutes was 3.2 L / min. After 5 hours, it was 3.1 L / min. Table 1 shows the results.
[0051]
(Comparative Example 3)
Using a phenolic fiber having a single fiber fineness of 2.2 dtex and a thread-like fineness of 295 dtex, a smooth knitted fabric was knitted by an 18 gauge double-sided circular knitting machine. This knitted fabric had a basis weight of 140 g / m 2 , a thickness of 1.10 mm, an apparent density of 0.14 g / cm 3 , and an air permeability of 174 cm 3 / cm 2 · s.
[0052]
This knit was carbonized in an inert atmosphere for 30 minutes from room temperature to 890 ° C. in the same manner as in Example 1, and then activated in an atmosphere containing 12% by mass of steam at a temperature of 890 ° C. for 90 minutes. The obtained knitted fibrous activated carbon knitted fabric had an absolutely dry basis weight of 140 g / m 2 , a thickness of 1.10 mm, and an air permeability of 174 cm 3 / cm 2 · s. The fibrous activated carbon knitted fabric had a toluene adsorption performance of 60 g / m 2 and a BET specific surface area of 1,330 m 2 / g.
[0053]
This knitted fibrous activated carbon knit was further heat-treated at 450 ° C. for 10 minutes in air in the same manner as in Example 2. The weight yield was 93% by mass, the absolute dry weight was 130 g / m 2 , the thickness was 1.10 mm, and the O / C ratio by XPS was 25. Further, the toluene adsorption capacity was 56 g / m 2 , the BET specific surface area was 1330 m 2 / g, and the gas permeability was 174 cm 3 / cm 2 · s.
[0054]
Further, as in Example 1, 5% by mass of activated carbon carrying a platinum catalyst was prepared. This platinum catalyst-supported activated carbon had a toluene adsorption performance of 43 g / m 2 , a BET specific surface area of 990 m 2 / g, and a gas permeability of 174 cm 3 / cm 2 · s. This platinum catalyst-supported activated carbon (10 cm 2) was reduced by vacuum drying at 120 ° C. for 12 hours, and the hydrogen gas generation rate (L / min) was measured. The hydrogen generation rate after 30 minutes was 2.2 L / min. After 5 hours, the flow rate was 2.0 L / min. Table 1 shows the results.
[0055]
[Table 1]
In Table 1, the values before carrying the catalyst represent the values after surface treatment of the fibrous activated carbon. In Comparative Examples 1 and 2, since the surface treatment was not performed, the values after carbonization and activation were calculated. Express.
[0057]
From the above results, the catalyst-supported activated carbons of Examples 1 to 4 have been subjected to surface treatment and have an O / C ratio of 10% or more, so that they generate a large amount of hydrogen gas and are used as good catalysts for dehydrogenation reactions and the like. be able to. On the other hand, the catalyst-carrying activated carbons of Comparative Examples 1 and 2 were not subjected to the surface treatment and had an O / C ratio of less than 10%, so that the amount of hydrogen gas generated was low.
[0058]
In addition, comparing Example 2 and Comparative Example 3, it can be seen that Example 2 clearly generates a larger amount of hydrogen than Comparative Example 3. Therefore, it is understood that milling is preferable to smooth knitting for the fibrous polymer. This is because milling knitting can achieve better air permeability than smooth knitting.
[0059]
The embodiments and examples disclosed this time are to be considered in all respects as illustrative and not restrictive. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.
[0060]
【The invention's effect】
As described above, the activated carbon carrier and the catalyst-supported activated carbon of the present invention have a high fibrous structure, in particular, a knitted structure, so that they have high air permeability, so that they have excellent thermal conductivity and hydrogen gas, hydrogenation or dehydrogenation reaction. Is excellent in diffusibility of reaction raw materials and products. Further, since the activated carbon carrier according to the present invention has an O / C ratio of 10% or more, the ability to support a catalyst is dramatically improved, and the reaction raw materials and products can be well diffused. For this reason, the catalyst-supporting activated carbon of the present invention can improve the reaction efficiency of the hydrogenation and dehydrogenation reactions, and can function as a high-performance catalyst carrier or catalyst.
[Brief description of the drawings]
FIG. 1 is a schematic diagram of a hydrogen generator used in the present invention.
[Explanation of symbols]
1 Round bottom flask, 2 activated carbon carrying catalyst, 3 electric heater, 4 cooling pipe, 5 cock, 6 hydrogen collecting pipe, 7 cooling pipe, 8 aromatic recovery section, 9 hydride introduction section with atomizer.
Claims (10)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111511682A (en) * | 2017-12-25 | 2020-08-07 | 株式会社可乐丽 | Activated carbon, metal-supporting activated carbon using same, and hydrogenation catalyst |
| CN115463648A (en) * | 2021-06-10 | 2022-12-13 | 中国科学院大连化学物理研究所 | Phosphine-containing organic polymer/active carbon composite carrier and preparation and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111511682A (en) * | 2017-12-25 | 2020-08-07 | 株式会社可乐丽 | Activated carbon, metal-supporting activated carbon using same, and hydrogenation catalyst |
| CN111511682B (en) * | 2017-12-25 | 2023-12-29 | 株式会社可乐丽 | Activated carbon, metal-supported activated carbon using same, and hydrogenation catalyst |
| CN115463648A (en) * | 2021-06-10 | 2022-12-13 | 中国科学院大连化学物理研究所 | Phosphine-containing organic polymer/active carbon composite carrier and preparation and application thereof |
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