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JP3029841B2 - 複合吸着材およびその製造方法 - Google Patents

複合吸着材およびその製造方法

Info

Publication number
JP3029841B2
JP3029841B2 JP2100128A JP10012890A JP3029841B2 JP 3029841 B2 JP3029841 B2 JP 3029841B2 JP 2100128 A JP2100128 A JP 2100128A JP 10012890 A JP10012890 A JP 10012890A JP 3029841 B2 JP3029841 B2 JP 3029841B2
Authority
JP
Japan
Prior art keywords
acid
amino acid
odor
aromatic amino
transition metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP2100128A
Other languages
English (en)
Other versions
JPH03296434A (ja
Inventor
和広 福本
正治 杉浦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyota Central R&D Labs Inc
Original Assignee
Toyota Central R&D Labs Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyota Central R&D Labs Inc filed Critical Toyota Central R&D Labs Inc
Priority to JP2100128A priority Critical patent/JP3029841B2/ja
Priority to US07/683,317 priority patent/US5231063A/en
Priority to DE4112296A priority patent/DE4112296A1/de
Publication of JPH03296434A publication Critical patent/JPH03296434A/ja
Priority to US08/020,111 priority patent/US5409769A/en
Application granted granted Critical
Publication of JP3029841B2 publication Critical patent/JP3029841B2/ja
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
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  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treating Waste Gases (AREA)

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、工場排ガス、生活環境において発生する煙
草臭、体臭、し尿臭、冷蔵庫の食品臭、あるいは自動車
の排ガス等に含まれるアンモニア、硫化水素、アセトア
ルデヒド等の悪臭の除去に有効な脱臭材に関する。
〔従来の技術〕
自動車、台所、居室内、事務所など生活環境に発生す
る悪臭は多種の悪臭が混合した複合臭である。例えば自
動車内の臭いは、煙草臭、汗臭、排ガス臭、ホコリ臭な
どが混合した複合臭で、その成分は数千種類にも及ぶと
言われている。悪臭防止法では、これらの臭気中の８種
類の成分、すなわちアンモニア、メチルメルカプタン、
硫化水素、硫化メチル、二硫化メチル、トリメチルアミ
ン、アセトアルデヒド、スチレンが特に重要な悪臭成分
として指定されている。
従来、このような悪臭を除去する方法としては、芳香
剤を利用してマスキングする方法、活性炭やシリカゲル
等で吸着除去する方法、などが採られてきた。
しかしながら、これらの方法にはそれぞれ欠点が存在
していた。芳香剤を用いてマスキングする方法は、悪臭
の成分を根本的に除去するというものではなく、また芳
香剤そのものの臭いも気になる場合がある。また、活性
炭やシリカゲル等物理吸着を利用する方法は、その吸着
材の種類で、吸着できる悪臭成分の種類が制限される。
例えば活性炭では、アンモニア、トリメチルアミンなど
の塩基性の臭気に対しては全く効果を示さなかった。
そこで、これらの欠点を解決する方法として、化学的
方法が考え出された。これは、中和反応により化学的に
悪臭を除去する方法であり、アセトアルデヒド、硫化水
素等の酸性臭気、アンモニア、トリメチルアミン等の塩
基性臭気の両者を同時に除去できる。
即ち、酸性臭気は塩基性吸着剤、塩基性臭気は酸性吸
着剤により中和して除去する。
しかしながら、塩基性吸着剤と酸性吸着剤はその性質
上、同一担体に同時に担持させた状態や、同一液体中に
同時に分散させた状態では、お互いに反応を起こし、失
活してしまうものであり、これが化学反応を利用した複
合吸着材の欠点となっていた。そこで従来の吸着材では
塩基性吸着剤と酸性吸着剤とを別々の担体に保持してい
たが、この場合には、各吸着剤の実質的な担持量が低下
し、これに伴って複合吸着材の脱臭性能も低下すること
となっていた。
〔発明の目的〕
そこで本発明の目的は、塩基性吸着剤であるアミノ酸
の酸性吸着剤である遷移金属塩とを同時に高分散状態で
共存させた新規な複合吸着材を提供することである。さ
らに詳しくは酸性臭気に対しても、塩基性臭気に対して
も、臭気の化学的性質にかかわらず、大きな吸臭性能を
発揮し、さらには化学的性質の異なる各吸着剤を同時に
担持することにより、複合活性化の弊害である担持量の
低下を防ぎ、脱臭能力に関しても単独の吸着剤を使用し
た時と同じ水準である複合吸着材を提供することにあ
る。
〔発明の構成〕
本発明者らは、このような従来の欠点を克服し、多種
の悪臭成分を含む複合臭に対し、優れた除去性能を発揮
する複合吸着材を開発すべく鋭意研究を重ねた結果、ｍ
−、またはｐ−芳香族アミノ酸の酸性塩、酸および遷移
金属化合物を有効成分として共存させた複合吸着材がき
わめて高い脱臭効果を示すことを見出した。
〔発明の作用〕
ｍ−、ｐ−芳香族アミノ酸の酸性塩は、酸性物質であ
るにもかかわらず、酸性臭気である低級アルデヒド類に
基づく悪臭ガスの除去に有効である。この性質は、アミ
ノ酸中の酸性塩化したアミノ基とカルボキシル基が同時
的且つ協奏的に作用し、低級アルデヒド類を化学的に吸
着除去あるいは化学的に不活性化することによって生ず
ると推定される。また、共存した酸は、一般によく知ら
れている酸塩基反応により、アンモニア、トリメチルア
ミンなど塩基性の悪臭ガスを除去する。
遷移金属化合物は、硫化水素やメチルメルカプタンな
ど硫化物系の悪臭ガスの除去に有効である。この性質
は、遷移金属化合物が硫化物系の悪臭ガスと化学反応
し、金属硫化物を生成することにより生ずる。
また、上記芳香族アミノ酸と遷移金属化合物とは芳香
族アミノ酸中の塩基性のアミノ酸と、酸性の遷移金属化
合物との酸塩基反応のために、通常安定には共存しな
い。しかしながら、芳香族アミノ酸を酸性塩とした場合
には、このアミノ基が加えた酸と塩を形成し、遷移金属
化合物との反応が生ぜず、両者の共存が可能となる。
さらに加えた酸は、上述のように塩基性悪臭ガスの除
去に有効である。従って、酸を過剰に加えることが芳香
族アミノ酸と遷移金属化合物との共存および塩基性悪臭
ガスの除去という２つのことを可能とした。
このように、上記の３種類以上から成る有効成分が相
互に化学的に反応しないため、これら有効成分を一度に
同時にかつ均一に多孔性担体に担持できるので、アンモ
ニア、硫化水素、およびアセトアルデヒドといった性質
の異なる悪臭ガスを効率よく除去することができる。
〔発明の効果〕
本発明の複合吸着材は、低級アルデヒド類に基づく悪
臭ガス、メチルメルカプタン、硫化水素などの硫化物系
の悪臭ガス、およびアンモニア、トリメチルアミンなど
の塩基性の悪臭ガスなどのいずれに対しても優れた除去
性能を示す。
従って、自動車、台所、居室内、事務所など生活環境
に発生する多種の悪臭成分を含む複合臭に対し、優れた
効果を発揮する実用上極めて有用性の高い複合吸着材で
ある。
〔その他の発明〕
ｍ−またはｐ−芳香族アミノ酸の酸性塩は以下のよう
につくることができる。即ち、ｍ−またはｐ−芳香族ア
ミノ酸、あるいは該アミノ酸の塩に酸を加えることによ
り、ｍ−またはｐ−芳香族アミノ酸のアミノ基にプロト
ンを供与し、アンモニウムイオンを形成させ、芳香族ア
ミノ酸の酸性塩とする。さらにこの時、酸を過剰に加え
ることにより、ｍ−、またはｐ−芳香族アミノ酸の酸性
塩と酸との共存物をつくることができる。
前記芳香族アミノ酸には、芳香族モノアミノモノカル
ボン酸が用いられる。芳香族モノアミノモノカルボン酸
として、好ましくはｍ−またはｐ−アミノ安息香酸、お
よびｐ−アミノサリチル酸が用いられる。
酸としては、塩酸、硝酸、硫酸、燐酸などの無機酸の
ほか、クエン酸、マロン酸、リンゴ酸、蓚酸などの有機
酸が挙げられ、高温下で使用する場合においては硫酸、
燐酸、蓚酸などの不揮発性の酸を用いることが好まし
い。
遷移金属化合物としては、ヒ素、水銀、銅、アンチモ
ン、ビスマス、すず、カドミウム、鉛、亜鉛、コバル
ト、ニッケル、鉄およびマンガンの硝酸塩、硫酸塩、炭
酸塩、燐酸塩、ピロリン酸塩、塩化物、臭化物、弗化物
などが挙げられ、中でも特に銅、亜鉛、コバルト、およ
びニッケルの塩化物、臭化物、弗化物が好適に使用され
る。
これらｍ−またはｐ−芳香族アミノ酸の酸性塩、酸、
および遷移金属化合物との共存物を本発明の複合吸着材
として使用する場合、その使用形態は特に制限されるも
のではなく、これらを粉末のまま使用することもできる
が、その効果を高めるためには任意の濃度の溶液とする
か、あるいは多孔性担体に担持させて使用することが有
効である。
多孔性担体としては、セピオライト、パリゴルスカイ
ト、活性炭、ゼオライト、活性炭素繊維、活性アルミ
ナ、セピオライト混合紙、シリカゲル、活性白土、バー
ミキュライト、ケイソウ土などの無機質多孔性担体のほ
か、パルプ、繊維、布、高分子多孔体などの有機質多孔
性担体などが使用できる。好ましくは、セピオライト、
パリゴルスカイト、活性炭、活性アルミナまたはゼオラ
イトが使用される。
本発明の有効成分をこれら多孔性担体に高分散状態で
生存担持させる。多孔性担体は、有効成分をその構造中
に有する細孔内に均一に保持し、悪臭ガスとの接触面積
を広げ、これら有効成分による悪臭ガスの吸着性能を向
上させる。また、多孔性担体自身が有する吸着能により
吸着材の悪臭除去性能がさらに向上する。例えば、活性
炭は炭化水素類に基づく悪臭ガスを、セピオライトは低
級脂肪酸類に基づく悪臭ガスをよく吸着する。
なお、多孔性担体の形状は、シート状、ハニカム状、
粉末状、粒状、顆粒状、板状、繊維状のいずれでもよ
い。
ｍ−、またはｐ−芳香族アミノ酸の酸性塩、酸および
遷移金属化合物の共存物を前記多孔性担体に担持する手
法は特に問わないが、好ましくはｍ−、またはｐ−芳香
族アミノ酸の酸性塩、酸および遷移金属化合物の共有物
を微粉砕して多孔性担体の微粉末に混合して成形して担
持する。より好ましくは、水またはその他の可溶性溶媒
に溶解し、その溶液を多孔性担体に含浸させ、担持す
る。このように溶液状で使用することにより、芳香族ア
ミノ酸の酸性塩、酸および遷移金属化合物を同時に多孔
性担体に均一に分散担持させることができ、これらの有
する脱臭性能を最大限に発揮させることができる。
ｍ−、またはｐ−芳香族アミノ酸の酸性塩、酸および
遷移金属化合物を同時に多孔性担体に担持する量は、担
体に対し該共存物の総量が0.1〜30重量％の範囲とする
ことが好ましい。
担持量が0.1重量％未満であるとアンモニア、アセト
アルデヒド、および硫化水素等の臭気の除去効果が小さ
く、30重量％を超えると多孔性担体へ分散性が悪くな
り、アンモニア、アセトアルデヒド、および硫化水素等
の臭気に対する除去性能も低下するばかりか、多孔性担
体それ自体が有する各種ガス吸着性能も低下する。より
好ましくは0.5〜15重量％の範囲で担持するのがよい。
なお、芳香族アミノ酸の酸性塩、酸および遷移金属化
合物から成る共存物の各成分の配合割合、および該共存
物を担持する多孔性担体は、発生する悪臭の主要成分に
よって、適当な配合割合および多孔性担体を選ぶことが
できる。
以下、本発明を実施例により詳細に説明するが、本発
明はその要旨を超えない限りこれら実施例により何等限
定されるものではない。
〔実施例〕
第１表に示した様に所定の芳香族アミノ酸、酸、およ
び遷移金属化合物を水に溶解し、芳香族アミノ酸の酸性
塩、酸および遷移金属化合物が共存する水溶液を作製し
た。なお、本実施例では、該共存物をつくる際、芳香族
アミノ酸の酸性塩を直接に用いず、芳香族アミノ酸に過
剰の酸を加えることによって芳香族アミノ酸のアミノ基
にプロトンを供与し、アンモニウムイオンを形成させ、
芳香族アミノ酸の各種酸性塩を形成させた。
次に、この水溶液を粒度４〜６メッシュのヤシガラ活
性炭300gに含浸させた後、100℃で10時間加熱乾燥して
本実施例の複合吸着材を得た（試料No.1〜５）。
得られた複合吸着材について、アセトアルデヒド、ア
ンモニア、および硫化水素の除去性能試験を次のように
して行った。
複合吸着材（試料No.1〜５）をそれぞれ1g秤量し、５
容量のガス非透過性の袋に入れた。この袋に425ppmア
セトアルデヒド、900ppmアンモニア、および10000ppm硫
化水素をそれぞれ導入して密封し、室温で放置した。24
時間後に袋内に残留したアセトアルデヒド、アンモニア
および硫化水素の濃度を測定した。結果を除去率（％）
として求めた。測定は、アセトアルデヒドについてはガ
スクロマトグラフ、アンモニアおよび硫化水素について
は北川式ガス検知管によった。第２表にガスクロマトグ
ラフの測定条件を、第３表に測定結果を示した。
比較のため、塩化第二銅のみ担持したもの、Ｏ−アミ
ノ安息香酸のみ担持したものもそれぞれについて、同様
にしてアセトアルデヒド、アンモニアおよび硫化水素に
対する除去性能試験を行った。結果を試料No.C−１、Ｃ
−２として第３表に併記する。
なお、除去率は下記（１）式により求めた。
ここでブランク濃度は、吸着材を袋に入れないで同様
の処理を行った場合の残留濃度であり、アセトアルデヒ
ド、アンモニアおよび硫化水素のブランク濃度はそれぞ
れ401.1ppm、820ppm、および7200ppmであった。
第３表の結果から明らかなように本実施例の複合吸着
材は、比較品に比べ、飛躍的に性能が向上した。
フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 20/22 A61L 9/01 B01D 53/38 B01D 53/81

Claims (4)

    (57)【特許請求の範囲】
  1. 【請求項１】ｍ−及び／又はｐ−芳香族アミノ酸の酸性
    塩、酸、および遷移金属化合物を有効成分として共存さ
    せた複合吸着材。
  2. 【請求項２】多孔性担体に、請求項（１）記載の各成分
    を高分散状態で共存担持した複合吸着材。
  3. 【請求項３】ｍ−及び／又はｐ−芳香族アミノ酸あるい
    は該アミノ酸の塩に酸を過剰添加するとともに、該遷移
    金属化合物を添加することにより、該アミノ酸の酸性
    塩、該酸および該遷移金属化合物が共存する請求項
    （１）または（２）記載の複合吸着材の製造方法。
  4. 【請求項４】前記芳香族アミノ酸が芳香族モノアミノモ
    ノカルボン酸であることを特徴とする請求項（１）また
    は（２）記載の複合吸着材。
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