JP3766771B2

JP3766771B2 - Adsorbent

Info

Publication number: JP3766771B2
Application number: JP31721199A
Authority: JP
Inventors: 政憲山中; 一男浅田
Original assignee: Japan Enviro Chemicals Ltd
Current assignee: Japan Enviro Chemicals Ltd
Priority date: 1999-11-08
Filing date: 1999-11-08
Publication date: 2006-04-19
Anticipated expiration: 2019-11-08
Also published as: JP2001129392A

Description

【０００１】
【発明の属する技術分野】
本発明は、比較的吸着し易い炭化水素類だけでなく、吸着の困難な酸性ガス（硫化水素、メチルメルカプタン等のメルカプタン類）、硫黄系中性ガス（ジメチルスルフィドやジメチルスルフィド類のスルフィド類）、塩基性ガス（アンモニアやトリメチルアミン等のアミン類）等が共存する悪臭ガスを、同時にかつ長時間にわたり吸着する優れた下水処理場の脱臭用吸着剤に関する。
【０００２】
【従来の技術】
従来多種の悪臭ガスを同時に吸着する技術としては、たとえばヨウ化カリウム等の金属ハロゲン化物とリン酸などの無機酸を同時に担持せしめたもの（特開昭５７−９９３３４号）、臭素等ハロゲンとリン酸などの無機酸を同時に担持せしめたもの（特開平０６−１２６１６６号）などが提案されている。また、それぞれ単独で担持せしめた悪臭ガス除去剤を決められた順番で組み合わせるという方法に関する技術（特開昭５５−５１４２２号）も知られている。しかしながら、吸着するべき悪臭物質の数が増加している昨今では、それに対応する吸着剤の種類の増加に伴い、既設の吸着設備では容量的に吸着剤を収容しきれない。また新設の設備においては吸着剤量が増加する等が問題となっており、さまざまな悪臭ガスに対応できる高性能の吸着剤が要望されている。
【０００３】
【発明が解決しようとする課題】
本発明の課題は、酸性ガス（硫化水素、メルカプタン類）、硫黄系中性ガス（スルフィド類）、塩基性ガス（アンモニア、アミン類）等多種類の吸着困難な悪臭ガスが共存するガスからこれらを同時に且つ長期に亘り吸着しうる下水処理場の脱臭用吸着剤を提供することにある。
【０００４】
【課題を解決するための手段】
前記の課題を解決するために、本発明者らは種々検討を重ねた結果、活性炭にこれまで用いられてきた複数の悪臭ガス吸着剤の各担持成分を同時に担持させることによって、これまでの吸着剤より単位体積当たりの吸着性能に優れ、且つ１つの吸着剤で多種のガスを同時に吸着しうるという知見を得た。この知見を基に、さらに研究を重ね本発明を完成した。
すなわち、本発明は、
（１）活性炭に、臭素、硫酸およびアルカリ金属ハロゲン化物を均一に担持させてなる下水処理場の脱臭用吸着剤、
（２）アルカリ金属ハロゲン化物がアルカリ金属ヨウ化物である（１）記載の吸着剤、
（３）アルカリ金属ヨウ化物がヨウ化カリウムである（２）記載の吸着剤、
（４）活性炭１００重量部に対し、臭素を０．１〜３０重量部、硫酸を１〜４０重量部およびアルカリ金属ハロゲン化物を０．０１〜５重量部担持させてなる（１）記載の吸着剤、
である。
【０００５】
【発明の実施の形態】
活性炭の原料としては、たとえば木粉、ヤシ殻などの植物原料、無煙炭、石油ピッチ、コークス等の石炭、石油系原料、アクリル樹脂、フェノール樹脂、エポキシ樹脂、ポリエステル樹脂などの合成樹脂系原料などが挙げられるが、ヤシ殻から得られるヤシ殻炭や無煙炭、石油ピッチ、コークス等の石炭が好適に用いられる。前述の活性炭原料は、たとえば固定床、移動床、流動床などで賦活化される。賦活化は、たとえば水蒸気、塩素、塩化水素、一酸化炭素、二酸化炭素、酸素等を用いるガス賦活、アルカリ、酸または塩化亜鉛などの薬品を用いる薬品賦活などがあるが、本発明に用いられる活性炭はそのいずれによって賦活化されたものでもよい。
【０００６】
本発明に用いられる活性炭は、液体窒素温度条件下の窒素吸着によるＢＥＴ比表面積が３００〜３，０００ｍ^２／ｇ、好ましくは５００〜２，０００ｍ^２／ｇのものである。
活性炭の粒子径は、通常０．０１〜１５ｍｍ、好ましくは０．１〜１０ｍｍ、その細孔径は通常１．０〜１０．０ｎｍ、好ましくは１．５〜５．０ｎｍ、その細孔容積は通常０．１〜１．５ｍｌ／ｇ、好ましくは０．２〜１．０ｍｌ／ｇである。
【０００７】
活性炭の形状は、例えば粉末状、破砕状、繊維状あるいは円柱状、球状、ハニカム状等に成型されたものであってもよい。
【０００８】
前述の活性炭の形状がハニカムである場合、そのセル数は１０〜１，５００個／inch^２、好ましくは２５〜７５０個／inch^２であり、厚みは５ｍｍ以上／個、好ましくは７．５ｍｍ以上／個であり、通気抵抗が小さいため、これらを複数個組み合わせても使用可能である。
本発明おいては、活性炭に、臭素、硫酸およびアルカリ金属ハロゲン化物を同時に、または順次担持させる。
活性炭に臭素を担持させる方法としては、
１）常温下で、液体である臭素（９９％）もしくは臭素含有水溶液を気化させ、窒素等のキャリヤーガスを用いて、容器内に充填した活性炭層に流通接触させる方法、
２）常温下で臭素もしくは臭素含有水溶液に活性炭を浸漬し、必要に応じて乾燥する方法、
３）噴霧器、散布器を用いて液体臭素または臭素含有水溶液を常温下で活性炭に直接散布もしくは窒素などのキァリアーガスを用いて噴霧し、必要に応じて乾燥する方法、
４）臭素を活性炭と共に容器内に静置し、常温下で気化させ、含侵させる方法、がある。
【０００９】
臭素の担持量は、活性炭１００重量部に対し、通常０．１〜３０重量部、好ましくは、１〜２０重量部である。
硫酸の活性炭への担持方法としては、たとえば、
１）活性炭を常温下で硫酸水溶液に浸漬し乾燥する方法、
２）活性炭に常温下で硫酸水溶液を噴霧器または散布器を用いて直接散布、又は窒素等のキャリアーガスとともに噴霧し、乾燥する方法などがある。
硫酸の活性炭１００重量部に対する担持量は、通常１〜４０重量部、好ましくは５〜３０重量部である。
本発明に用いられるアルカリ金属ハロゲン化物のアルカリ金属としては、たとえばナトリウム、カリウム、リチウムなどが挙げられるが、カリウムが好ましく、ハロゲンとしては、臭素またはヨウ素などが挙げられるが、ヨウ素が好ましい。アルカリ金属ハロゲン化物としては、例えばヨウ化カリウム、ヨウ化ナトリウムなどが挙げられるが、ヨウ化カリウムが好ましい。
【００１０】
これらのアルカリ金属ハロゲン化物の活性炭への担持方法としては、たとえば、
１）活性炭を常温下アルカリ金属ハロゲン化物の水溶液に浸漬して、乾燥する方法や、
２）活性炭に常温下アルカリ金属ハロゲン化物の水溶液を噴霧器または散布器を用いて直接散布又は窒素等のキャリアーガスとともに噴霧する方法が挙げられる。
これらのアルカリ金属ハロゲン化物の活性炭１００重量部に対する担持量は、通常０．０１〜５重量部、好ましくは０．１〜１重量部である。
臭素、硫酸およびアルカリ金属ハロゲン化物の活性炭への担持は、二種以上を同時に行っても良く、任意の順序で順次行っても良い。
本発明における臭素、硫酸およびアルカリ金属ハロゲン化物は、それぞれ活性炭に均一に担持されていることが必要である。ここに「均一」とは、吸着剤の試料を任意に抽出した場合、その試料の担持物質の含量が実質的に等しいことを云う。担持物質をそれぞれを単独に担持させた活性炭を層状に組み合わせたり、また混合したものでは所期の目的は達成できない。
【００１１】
本発明の吸着剤は、硫化水素、メチルメルカプタンなどのメルカプタン類、ジメチルスルフィドやジメチルジスルフィド等のスルフィド類、アンモニア、モノメチルアミン、ジメチルアミン、トリメチルアミンなどのアミン類など吸着の困難な悪臭ガスが共存するガスから、それらを同時に、単位体積当たりで換算して高い効率で、且つ長時間に亘り吸着することができる。
被処理悪臭ガスの空間速度は、悪臭ガス濃度、吸着剤の形状により異なってくるが、例えば２０〜５００，０００ｈｒ^−１、好ましくは１００〜１００，０００ｈｒ^−１程度である。
さらに乾燥時や使用時に刺激臭を発することもなく、多孔質担体が活性炭の場合も発火点が低くなることもない。したがって本吸着剤は下水処理場の脱臭装置に安全に使用することができる。
【００１２】
【実施例】
以下に実施例、比較例、参考例、試験例を挙げて本発明をさらに具体的に説明するが、本発明はこれらに限定されるものではない。
実施例１
ヨウ化カリウム０．２５ｇを蒸留水２１．５４ｇに溶解し、ヨウ化カリウム水溶液を調製した。また４７％硫酸３０．０３ｇを蒸留水１５．０５ｇに溶解し、硫酸水溶液を調製した。ＢＥＴ法による比表面積が１６００ｍ^２、平均細孔径が１．８ｎｍ、細孔容積が０．５５ｍｌ／ｇで粒子径が０．８５〜１．７０ｍｍの破砕状ヤシ殻活性炭１５０ｇを２リットル容量のフラスコ内に静置し、頂部から吊したサンプル瓶の中に臭素５．００ｇを注入し、容器を密栓し、常温下で気化した臭素ガスを活性炭と２４時間接触させ含侵させた。
次いで、臭素を含侵させた活性炭を、２リットル容量のポリプロピレン容器に入れ、卓上ミキサーで撹拌（１００〜３００ｒｐｍ）しながら、先に調製した各水溶液の全量をそれぞれ窒素気流下に噴霧し、臭素、ヨウ化カリウム、硫酸担持活性炭を得た。得られた担持活性炭２２．８ｍｌを内径１５．６ｍｍのガラス製カラムに充填した。
【００１３】
実施例２
ヨウ化カリウム０．２５ｇを蒸留水２１．５４ｇに溶解し、ヨウ化カリウム水溶液を調製した。また４７％硫酸３０．０３ｇを蒸留水１５．０５ｇに溶解し、硫酸水溶液を調製した。ここで実施例１で用いたと同じ破砕状ヤシ殻活性炭１２５ｇを２リットル容量のフラスコ内に静置し、実施例と同様にして臭素５．００ｇを活性炭と接触させて含侵させた。次いで、臭素を含侵させた活性炭を、実施例１と同様にして、先に調製した各水溶液の全量をそれぞれ噴霧し、臭素、ヨウ化カリウム、硫酸担持活性炭を得た。得られた担持活性炭１９．０ｍｌを内径１５．６ｍｍのガラス製カラムに充填した。
【００１４】
実施例３
ヨウ化カリウム０．２５ｇを蒸留水２１．５４ｇに溶解し、ヨウ化カリウム水溶液を調製した。また４７％硫酸３０．０９ｇを蒸留水１５．０５ｇに溶解し、硫酸水溶液を調製した。ここで実施例１で用いたと同じ破砕状ヤシ殻活性炭１２５ｇを２リットル容量のフラスコ内に静置し、実施例１と同様にして臭素５．００ｇを活性炭と接触させて含侵させた。次いで、臭素を含侵させた活性炭を、実施例１と同様にして、先に調製した各水溶液の全量をそれぞれ噴霧し、臭素、ヨウ化カリウム、硫酸担持活性炭を得た。得られた担持活性炭１５．２ｍｌを内径１５．６ｍｍのガラス製カラムに充填した。
【００１５】
参考例１
ヨウ化カリウム０．２５ｇを蒸留水２１．５４ｇに溶解し、ヨウ化カリウム水溶液を調製した。また８５％リン酸１６．６０ｇを蒸留水２８．４８ｇに溶解し、リン酸水溶液を調製した。実施例１で用いたと同じ破砕状ヤシ殻活性炭１５０ｇを２リットル容量のフラスコ内に静置し、実施例１と同様にして臭素５．００ｇを活性炭と接触させ含侵させた。次いで、臭素を含侵させた活性炭を、実施例１と同様にして、先に調製した各水溶液の全量をそれぞれ噴霧し、臭素、ヨウ化カリウム、リン酸担持活性炭を得た。得られた担持活性炭１５．２ｍｌを内径１５．６ｍｍのガラス製カラムに充填した。
【００１６】
比較例１
ヨウ化カリウム０．５ｇを蒸留水４３．０７ｇに溶解し、ヨウ化カリウム水溶液を調製した。また４７％硫酸６０．０ｇを蒸留水３０．０７ｇに溶解し、硫酸水溶液を調製した。実施例１で用いたと同じ破砕状ヤシ殻活性炭１００ｇを２リットル容量のフラスコ内に静置し、実施例１と同様の方法で臭素１０ｇを活性炭に含侵させて臭素担持活性炭を得た。別途用意した同じ性状の活性炭１００ｇを実施例１と同様にして、先に調製したヨウ化カリウム水溶液を噴霧し、ヨウ化カリウム担持活性炭を得た。さらに別途用意した同じ性状の活性炭１００ｇを実施例１と同様にして、先に調製した硫酸水溶液を噴霧して硫酸担持活性炭を得た。得られた各々の担持活性炭の７．６ｍｌずつを均一に混合して、２２．８ｍｌの混合試料を調製し、内径１５．６ｍｍのガラス製カラムに充填した。
【００１７】
比較例２
ヨウ化カリウム０．５ｇを蒸留水４３．０７ｇに溶解し、ヨウ化カリウム水溶液を調製した。また４７％硫酸６０．０ｇを蒸留水３０．０７ｇに溶解し、硫酸水溶液を調製した。以下比較例１と同様にして、臭素担持活性炭、ヨウ化カリウム担持活性炭および硫酸担持活性炭を得た。得られた各々の担持活性炭をガス流通方向に正対してヨウ化カリウム担持炭、硫酸担持炭、臭素担持炭の順にガラスウールを層間に挟んで７．６ｍｌずつ内径１５．６ｍｍのカラム内に充填し、３層からなる試料を調製した。
【００１８】
試験例１（悪臭ガス吸着性能測定試験）
２５℃に保たれた恒温槽内に、〔図１〕に示される吸着性能測定装置を設置し、内径１５．６ｍｍのガラス製カラムに充填した実施例１〜３、参考例１、比較例１および２で得られた試料を調製した。
【表１】

【００１９】
上記試料充填カラムに、相対湿度８０％に調製した空気標準ガスボンベから、悪臭ガスを同伴させてそれぞれのガス濃度がジメチルスルフィド１０ｐｐｍ（ｖ／ｖ）、アンモニア３０ｐｐｍ（ｖ／ｖ）および硫化水素２０ｐｐｍ（ｖ／ｖ）となる悪臭ガスを調製し、このガスを流量２．３リットル／分、線速度２０ｃｍ／秒で流通させ、各ガスの入口濃度に対する出口濃度を測定した。得られた破過曲線から比較例２の試料の吸着性能を１．００とする活性炭の試料の吸着性能比を次式により算出した。測定は、硫黄系ガス（硫化メチル、硫化水素）の場合は島津ガスクロマトグラフＧＣ−１４Ｂ（ＦＰＤ検出器付き）を用いて分析した。カラムには硫黄系ガスを分離できる充填カラム（β−β′ＯＤＰＮ２５％）を用いて行った。
一方、アンモニアの場合は（株）ガステック製検知管アンモニア用Ｎｏ．３Ｌ（１〜３０ｐｐｍ（ｖ／ｖ））を用いて、ガスを１００ｍｌ吸引した際の検知管の目盛りを読み、ガス流通時間に対する除去率を次式により算出した。
【数１】

また得られた結果から各試料の５％破過時間（処理前ガス濃度に対する処理後ガス濃度の比が５％に達した時間、すなわちリークしたガスの濃度が入口濃度の５％に達した時間）と活性炭の試料の吸着性能比及び各試料の単位容積あたりの吸着性能比を比較例２の試料の吸着性を１．００として算出した。それらの結果を〔表２〕〜〔表４〕に示す。
【００２０】
【表２】

【００２１】
【表３】

【００２２】
【表４】

実施例１〜３、参考例１の吸着剤は、比較例１の単成分担持吸着剤の混合物および比較例２の単成分担持３層吸着剤に比してジメチルスルフィド、アンモニア、硫化水素のいずれの吸着率も高く、各悪臭成分の５％破過時間、吸着性能比、単位容積当たりの吸着性能のいずれにおいても優れていた。特に実施例２および３の３成分担持吸着剤は、単位容積当たりの吸着性能が飛躍的に向上した。
【００２３】
【発明の効果】
本発明の吸着剤は、活性炭に、臭素、硫酸およびアルカリ金属ハロゲン化物を同時に担持させたことにより、酸性ガス（硫化水素、メルカプタン類）、硫黄系中性ガス（スルフィド類）、塩基性ガス（アンモニア、アミン類）など多種類の吸着困難な悪臭ガスが共存するガスからこれらを同時に且つ長期に亘り脱臭することができる。また単位体積当たりの吸着性能は従来の吸着剤に比して飛躍的に向上した
【図面の簡単な説明】
【図１】悪臭ガス吸着性能測定に用いた装置のフローシート。
【符号の説明】
Ａ：エアーサプライヤー
Ｂ：マスフローコントローラー
Ｃ：水蒸気発生ビン
Ｄ：ガスボンベ
Ｅ：ガス混合ビン
Ｆ：試料
Ｇ：吸着カラム
Ｈ：流量計[0001]
BACKGROUND OF THE INVENTION
In the present invention, not only hydrocarbons that are relatively easily adsorbed, but also acidic gases that are difficult to adsorb (mercaptans such as hydrogen sulfide and methyl mercaptan), sulfur-based neutral gases (sulfides such as dimethyl sulfide and dimethyl sulfide) Furthermore, the present invention relates to an excellent deodorizing adsorbent for sewage treatment plants that adsorbs malodorous gases coexisting with basic gases (amines such as ammonia and trimethylamine) at the same time for a long time.
[0002]
[Prior art]
Conventional techniques for simultaneously adsorbing various malodorous gases include, for example, a metal halide such as potassium iodide and an inorganic acid such as phosphoric acid supported simultaneously (Japanese Patent Laid-Open No. 57-99334), halogen such as bromine and phosphorus. A material in which an inorganic acid such as an acid is simultaneously supported (Japanese Patent Laid-Open No. 06-126166) has been proposed. In addition, a technique (Japanese Patent Laid-Open No. 55-51422) relating to a method in which malodorous gas removing agents carried independently are combined in a predetermined order is also known. However, in recent years when the number of malodorous substances to be adsorbed is increasing, with the increase in the types of adsorbents corresponding thereto, the existing adsorbing equipment cannot accommodate the adsorbents in volume. In addition, an increase in the amount of adsorbent is a problem in newly installed equipment, and a high-performance adsorbent that can cope with various malodorous gases is desired.
[0003]
[Problems to be solved by the invention]
The problem of the present invention is that gases such as acid gases (hydrogen sulfide, mercaptans), sulfur-based neutral gases (sulfides), basic gases (ammonia, amines), etc., which coexist with a variety of difficult-to-adsorb odorous gases. simultaneously and to provide a deodorizing adsorbent adsorbed cormorants Ru sewage treatment plants for a long time.
[0004]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors have made various studies. As a result, the activated carbon is supported by simultaneously supporting each supported component of the plurality of malodorous gas adsorbents used so far on activated carbon. The present inventors have found that the adsorption performance per unit volume is superior to that of the adsorbent and that various gases can be adsorbed simultaneously with one adsorbent. Based on this knowledge, the present invention was completed by further research.
That is, the present invention
(1) activated carbon, bromine, sulfate and an alkali metal halide deodorizing adsorbent sewage treatment plants ing uniformly by supporting,
( 2 ) The adsorbent according to (1), wherein the alkali metal halide is an alkali metal iodide,
( 3 ) The adsorbent according to ( 2 ), wherein the alkali metal iodide is potassium iodide,
(4) 100 parts by weight of activated carbon with respect to, 0.1 to 30 parts by weight of bromine, formed by the the sulfuric acid 1 to 40 parts by weight of alkali metal halide is from 0.01 to 5 parts by weight carrier (1) according Adsorbent,
It is.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Examples of activated carbon materials include plant materials such as wood powder and coconut shells, coals such as anthracite, petroleum pitch and coke, petroleum-based materials, synthetic resin-based materials such as acrylic resins, phenolic resins, epoxy resins, and polyester resins. Although mentioned, coals, such as coconut shell charcoal obtained from coconut shell, anthracite, petroleum pitch, and coke, are used suitably. The aforementioned activated carbon raw material is activated, for example, in a fixed bed, a moving bed, a fluidized bed, or the like. The activation includes, for example, gas activation using water vapor, chlorine, hydrogen chloride, carbon monoxide, carbon dioxide, oxygen, etc., chemical activation using chemicals such as alkali, acid or zinc chloride, etc., but the activated carbon used in the present invention May be activated by any of them.
[0006]
Activated carbon used in the present invention, BET specific surface area by nitrogen adsorption of liquid nitrogen temperature conditions 300~3,000m ² / g, preferably at the 500~2,000m ² / g.
The particle diameter of the activated carbon is usually 0.01 to 15 mm, preferably 0.1 to 10 mm, the pore diameter is usually 1.0 to 10.0 nm, preferably 1.5 to 5.0 nm, and the pore volume is usually 0.1~1.5ml / g, Ru preferably 0.2~1.0ml / g der.
[0007]
The shape of the activated carbon may be, for example, a powder shape, a crushed shape, a fiber shape, a cylindrical shape, a spherical shape, a honeycomb shape, or the like.
[0008]
When the shape of the activated carbon is a honeycomb, the number of cells is 10 to 1,500 cells / inch ² , preferably 25 to 750 cells / inch ² , and the thickness is 5 mm or more, preferably 7.5 mm or more. Since the ventilation resistance is small, a combination of a plurality of these can be used.
In the present invention comprise, activated carbon, bromine, sulfate and an alkali metal halide at the same time, or Ru is sequentially carried.
As a method of supporting bromine on activated carbon ,
1) A method of vaporizing a liquid bromine (99%) or a bromine-containing aqueous solution at normal temperature and using a carrier gas such as nitrogen to circulate and contact the activated carbon layer filled in the container,
2) A method in which activated carbon is immersed in bromine or a bromine-containing aqueous solution at room temperature, and dried as necessary.
3) A method of spraying liquid bromine or a bromine-containing aqueous solution directly on activated carbon at room temperature using a sprayer or sprayer, or spraying with a carrier gas such as nitrogen, and drying as necessary.
4) of bromine were placed in the vessel together with the activated carbon, it is vaporized at room temperature, a method of impregnating, there Ru.
[0009]
Supported amount of bromine, 100 parts by weight of activated carbon to usually 0.1 to 30 parts by weight, preferably, Ru 1-20 parts by der.
The method for supporting to activated carbon sulfate, for example,
1) a method of immersing dried sulfate aqueous solution with activated carbon at room temperature,
2) directly using a nebulizer or dispenser a sulfuric acid aqueous solution at room temperature activated carbon spraying, or sprayed with a carrier gas such as nitrogen, and a method of drying.
Loading amount with respect to 100 parts by weight of activated carbon sulfate is usually 1 to 40 parts by weight, preferably 5 to 30 parts by weight.
Examples of the alkali metal of the alkali metal halide used in the present invention include sodium, potassium, and lithium. Potassium is preferable, and examples of the halogen include bromine or iodine, but iodine is preferable. Examples of the alkali metal halide include potassium iodide and sodium iodide, and potassium iodide is preferable.
[0010]
As a method for supporting these alkali metal halides on activated carbon , for example,
1) A method in which activated carbon is immersed in an aqueous solution of an alkali metal halide at room temperature and dried,
2) A method of spraying an aqueous solution of an alkali metal halide on activated carbon directly at a room temperature using a sprayer or a sprayer or with a carrier gas such as nitrogen.
The supported amount of these alkali metal halides with respect to 100 parts by weight of activated carbon is usually 0.01 to 5 parts by weight, preferably 0.1 to 1 part by weight.
Bromine, supported to activated carbon sulfate and an alkali metal halide, may be carried out two or more thereof, may be performed sequentially in any order.
Bromine in the present invention, sulfuric acid and an alkali metal halide, it is necessary that it is uniformly supported on the respective activated carbon. Here, “uniform” means that when a sample of the adsorbent is arbitrarily extracted, the content of the support material in the sample is substantially equal. The desired purpose cannot be achieved by combining or mixing the activated carbons each carrying the support material in layers.
[0011]
The adsorbent of the present invention coexists with difficult-to-adsorb malodorous gases such as hydrogen sulfide, mercaptans such as methyl mercaptan, sulfides such as dimethyl sulfide and dimethyl disulfide, and amines such as ammonia, monomethylamine, dimethylamine and trimethylamine. From gas, they can be adsorbed over a long period of time with high efficiency in terms of unit volume.
Space velocity of the processing malodorous gases, malodorous gas concentration, but varies depending on the shape of the adsorbent, for example 20～500,000Hr ^-1, preferably about 100~100,000hr ^-1.
Further, no irritating odor is generated during drying or use, and the ignition point is not lowered even when the porous carrier is activated carbon. Accordingly, the present adsorbents can be safely used in the deodorizing apparatus of the sewage treatment plant.
[0012]
【Example】
EXAMPLES The present invention will be described more specifically with reference to examples, comparative examples, reference examples, and test examples, but the present invention is not limited to these examples.
Example 1
A potassium iodide aqueous solution was prepared by dissolving 0.25 g of potassium iodide in 21.54 g of distilled water. In addition, 30.03 g of 47% sulfuric acid was dissolved in 15.05 g of distilled water to prepare an aqueous sulfuric acid solution. A 2 liter flask containing 150 g of crushed coconut shell activated carbon having a specific surface area by BET method of 1600 m ² , an average pore size of 1.8 nm, a pore volume of 0.55 ml / g and a particle size of 0.85 to 1.70 mm Then, 5.00 g of bromine was poured into a sample bottle suspended from the top, the vessel was sealed, and bromine gas vaporized at room temperature was brought into contact with activated carbon for 24 hours to be impregnated.
Next, the activated carbon impregnated with bromine is placed in a 2 liter polypropylene container, and the total amount of each aqueous solution prepared above is sprayed under a nitrogen stream while stirring with a desktop mixer (100 to 300 rpm). Then, activated carbon carrying potassium iodide and sulfuric acid was obtained. The obtained supported activated carbon (22.8 ml) was packed in a glass column having an inner diameter of 15.6 mm.
[0013]
Example 2
A potassium iodide aqueous solution was prepared by dissolving 0.25 g of potassium iodide in 21.54 g of distilled water. In addition, 30.03 g of 47% sulfuric acid was dissolved in 15.05 g of distilled water to prepare an aqueous sulfuric acid solution. Here, 125 g of the same crushed coconut shell activated carbon used in Example 1 was allowed to stand in a flask having a capacity of 2 liters, and 5.00 g of bromine was brought into contact with activated carbon and impregnated in the same manner as in Example. Subsequently, the activated carbon impregnated with bromine was sprayed in the same manner as in Example 1 to spray the entire amount of each of the aqueous solutions prepared previously to obtain activated carbon supporting bromine, potassium iodide and sulfuric acid. 19.0 ml of the obtained supported activated carbon was packed in a glass column having an inner diameter of 15.6 mm.
[0014]
Example 3
A potassium iodide aqueous solution was prepared by dissolving 0.25 g of potassium iodide in 21.54 g of distilled water. Further, 30.09 g of 47% sulfuric acid was dissolved in 15.05 g of distilled water to prepare an aqueous sulfuric acid solution. Here, 125 g of the same crushed coconut shell activated carbon used in Example 1 was allowed to stand in a 2 liter flask, and 5.00 g of bromine was impregnated with activated carbon in the same manner as in Example 1. Subsequently, the activated carbon impregnated with bromine was sprayed in the same manner as in Example 1 to spray the entire amount of each of the aqueous solutions prepared previously to obtain activated carbon supporting bromine, potassium iodide and sulfuric acid. The obtained supported activated carbon 15.2 ml was packed in a glass column having an inner diameter of 15.6 mm.
[0015]
Reference example 1
A potassium iodide aqueous solution was prepared by dissolving 0.25 g of potassium iodide in 21.54 g of distilled water. Further, 16.60 g of 85% phosphoric acid was dissolved in 28.48 g of distilled water to prepare a phosphoric acid aqueous solution. 150 g of the same crushed coconut shell activated carbon used in Example 1 was allowed to stand in a 2 liter flask, and 5.00 g of bromine was brought into contact with the activated carbon and impregnated in the same manner as in Example 1. Subsequently, the activated carbon impregnated with bromine was sprayed in the same manner as in Example 1 to spray the entire amount of each of the aqueous solutions prepared previously to obtain bromine, potassium iodide, and phosphoric acid-supported activated carbon. The obtained supported activated carbon 15.2 ml was packed in a glass column having an inner diameter of 15.6 mm.
[0016]
Comparative Example 1
A potassium iodide aqueous solution was prepared by dissolving 0.5 g of potassium iodide in 43.07 g of distilled water. Further, 60.0 g of 47% sulfuric acid was dissolved in 30.07 g of distilled water to prepare a sulfuric acid aqueous solution. 100 g of the same crushed coconut shell activated carbon used in Example 1 was allowed to stand in a 2-liter flask, and 10 g of bromine was impregnated into the activated carbon in the same manner as in Example 1 to obtain a bromine-supported activated carbon. 100 g of activated carbon having the same properties prepared separately was sprayed with the previously prepared potassium iodide aqueous solution in the same manner as in Example 1 to obtain potassium iodide-supported activated carbon. Further, 100 g of activated carbon having the same properties prepared separately was sprayed with the previously prepared sulfuric acid aqueous solution in the same manner as in Example 1 to obtain sulfuric acid-supported activated carbon. 7.6 ml of each of the obtained supported activated carbons was uniformly mixed to prepare a 22.8 ml mixed sample, which was packed in a glass column having an inner diameter of 15.6 mm.
[0017]
Comparative Example 2
A potassium iodide aqueous solution was prepared by dissolving 0.5 g of potassium iodide in 43.07 g of distilled water. Further, 60.0 g of 47% sulfuric acid was dissolved in 30.07 g of distilled water to prepare a sulfuric acid aqueous solution. Thereafter, in the same manner as in Comparative Example 1, bromine-supported activated carbon, potassium iodide-supported activated carbon and sulfuric acid-supported activated carbon were obtained. Each obtained activated carbon is directly aligned in the gas flow direction and filled with 7.6 ml of a column having an inner diameter of 15.6 mm by sandwiching glass wool between the layers in the order of potassium iodide-supporting charcoal, sulfuric acid-supporting charcoal, and bromine-supporting charcoal. A sample consisting of three layers was prepared.
[0018]
Test Example 1 (Odor gas adsorption performance measurement test)
In the thermostat kept at 25 ° C., the adsorption performance measuring device shown in FIG. 1 was installed and filled in a glass column having an inner diameter of 15.6 mm , Reference Examples 1 and Comparative Example 1 Samples obtained in 2 and 2 were prepared.
[Table 1]

[0019]
From the air standard gas cylinder prepared at a relative humidity of 80%, the sample packed column was accompanied by malodorous gas, and the respective gas concentrations were 10 ppm (v / v) dimethyl sulfide, 30 ppm (v / v) ammonia, and 20 ppm hydrogen sulfide ( The malodorous gas which becomes v / v) was prepared, this gas was circulated at a flow rate of 2.3 liter / min and a linear velocity of 20 cm / sec, and the outlet concentration with respect to the inlet concentration of each gas was measured. From the obtained breakthrough curve, the adsorption performance ratio of the activated carbon sample where the adsorption performance of the sample of Comparative Example 2 was 1.00 was calculated by the following equation. In the case of sulfur-based gas (methyl sulfide, hydrogen sulfide), the measurement was analyzed using Shimadzu gas chromatograph GC-14B (with FPD detector). As the column, a packed column (β-β′ODPN 25%) capable of separating sulfur gas was used.
On the other hand, in the case of ammonia, No. for detector tube ammonia manufactured by Gastec Corporation. Using 3 L (1 to 30 ppm (v / v)), the scale of the detection tube when 100 ml of gas was sucked was read, and the removal rate with respect to the gas circulation time was calculated by the following equation.
[Expression 1]

From the obtained results, the 5% breakthrough time of each sample (the time when the ratio of the gas concentration after treatment to the gas concentration before treatment reached 5%, that is, the time when the concentration of leaked gas reached 5% of the inlet concentration) ) And the activated carbon sample adsorption performance ratio and the adsorption performance ratio per unit volume of each sample were calculated assuming that the adsorption property of the sample of Comparative Example 2 was 1.00. The results are shown in [Table 2] to [Table 4].
[0020]
[Table 2]

[0021]
[Table 3]

[0022]
[Table 4]

The adsorbents of Examples 1 to 3 and Reference Example 1 were any of dimethyl sulfide, ammonia, and hydrogen sulfide as compared with the mixture of the single component-supported adsorbent of Comparative Example 1 and the single-component-supported three-layer adsorbent of Comparative Example 2. The adsorption rate was also high, and each of the malodorous components was excellent in 5% breakthrough time, adsorption performance ratio, and adsorption performance per unit volume. In particular, the adsorption performance per unit volume of the three-component supported adsorbents of Examples 2 and 3 was dramatically improved.
[0023]
【The invention's effect】
Adsorbents of the present invention, the activated carbon, bromine, by was supported sulfuric acid and an alkali metal halide at the same time, acid gases (hydrogen sulfide, mercaptans), sulfur-based neutral gas (sulfide), basic gases These can be deodorized simultaneously and over a long period of time from gases coexisting with various kinds of malodorous gases that are difficult to adsorb such as (ammonia, amines). In addition, the adsorption performance per unit volume has improved dramatically compared to conventional adsorbents. [Brief description of the drawings]
FIG. 1 is a flow sheet of an apparatus used for measuring malodorous gas adsorption performance.
[Explanation of symbols]
A: Air supplier B: Mass flow controller C: Water vapor generation bottle D: Gas cylinder E: Gas mixing bottle F: Sample G: Adsorption column H: Flow meter

Claims

Activated carbon, deodorizing adsorbent sewage treatment plants ing uniformly by supporting bromine, sulfate and alkali metal halides.

The adsorbent according to claim 1, wherein the alkali metal halide is an alkali metal iodide.

The adsorbent according to claim 2 , wherein the alkali metal iodide is potassium iodide.

100 parts by weight of activated carbon with respect to, 0.1 to 30 parts by weight of bromine, a sulfuric acid 1 to 40 parts by weight of an alkali metal halide comprising by 0.01 to 5 parts by weight carrier according to claim 1 adsorbent according.