JP3571440B2 - Fibrous activated carbon for aliphatic aldehyde adsorption - Google Patents
Fibrous activated carbon for aliphatic aldehyde adsorption Download PDFInfo
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- JP3571440B2 JP3571440B2 JP33150395A JP33150395A JP3571440B2 JP 3571440 B2 JP3571440 B2 JP 3571440B2 JP 33150395 A JP33150395 A JP 33150395A JP 33150395 A JP33150395 A JP 33150395A JP 3571440 B2 JP3571440 B2 JP 3571440B2
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- Prior art keywords
- activated carbon
- fibrous activated
- aliphatic aldehyde
- aliphatic
- aminoacetanilide
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Description
【０００１】
【発明の属する技術分野】
本発明は，タバコ臭の主な原因物質である脂肪族アルデヒド消臭用として好適な脂肪族アルデヒド吸着用繊維状活性炭に関するものである。
【０００２】
【従来の技術】
近年，オフィスや個人用住居等には， 断熱アルミサッシ，冷暖房設備， 防音設備等が完備したものが増えているが，生活様式の変化に伴う居住空間の気密化は，オフィス，家庭等の空間に種々の臭いの問題を生み出している。その中の１つとして， 室内空気のタバコ臭が挙げられる。
【０００３】
タバコ臭の主な原因物質は脂肪族アルデヒドであるが，脂肪族アルデヒド吸着材としては，例えば，アニリン等の芳香族１級アミンを活性炭に添着したもの（特公昭６０−５４０９５号公報， 特開平７−１３６５０２号公報），芳香族アミンの酸性塩を活性炭に添着したもの（特開平６−２２５９２７号公報），ポリアルキレンイミンと非イオン性の吸湿性有機物質（ポリエチレングリコール等）を粉末状活性炭に保持させたもの（特公平４−３５７４０号公報）等が提案されている。
【０００４】
上記の脂肪族アルデヒド吸着材のうち，アニリン等の芳香族アミンを使用したものは，添着時の作業性，再脱離による室内の汚染等による安全性の問題がある。また，芳香族アミンやポリアルキレンイミンを使用したものは，脂肪族アセトアルデヒド吸着性能が経時的に劣化し，一度使用した後， 水で洗浄して再使用に供すると，脂肪族アセトアルデヒド吸着性能が低下するなど吸着効果も満足できるものではない。さらに，抄紙等の湿式加工法では，添着物質が水中に溶け出し，吸着性能の低いものしか得られないので，加工方法も特定の方法に限定されるという欠点がある。
【０００５】
【発明が解決しようとする課題】
本発明は，上記の問題を解決し， 脂肪族アルデヒド消臭用途において優れた性能を示し，経時的な性能劣化や洗浄による性能の劣化が非常に少ない脂肪族アルデヒド吸着用繊維状活性炭を提供することを技術的な課題とするものである。
【０００６】
【課題を解決するための手段】
本発明者らは、上記の課題を解決するために鋭意検討した結果、液相酸化処理あるいは気相酸化処理を施し、特定比率の酸性官能基を表面に導入した繊維状活性炭に、ｐ−アミノアセトアニリドを添着させれば、脂肪族アルデヒドに対して優れた吸着性能を示し、再脱離による空気の汚染、や経時的あるいは加工上の性能劣化の少ない繊維状活性炭が得られることを知見して本発明に到達した。
【０００７】
すなわち、本発明は、酸化処理を施して酸性官能基を導入した表面酸素濃度が10〜20％の繊維状活性炭に、ｐ−アミノアセトアニリドを添着させてなることを特徴とした脂肪族アルデヒド吸着用繊維状活性炭を要旨とするものである。
本発明において、表面酸素濃度は、ＥＳＣＡによる表面元素定量分析で求めるものである。
【０００８】
【発明の実施の形態】
以下，本発明について詳細に説明する。
【０００９】
本発明の脂肪族アルデヒド吸着用繊維状活性炭は、酸化処理を施した繊維状活性炭に、ｐ−アミノアセトアニリドを添着させたものであるが、本発明で用いる繊維状活性炭としては、再生セルロース系、アクリル繊維系、フェノール樹脂（ノボラック）系、ピッチ系等のものが挙げられる。また、繊維状活性炭の比表面積は大きい程、高い性能が得られるが、実用的には700〜2000m2/gのものが好ましく、細孔直径は10〜30Å、細孔容積は0.25〜1.30m3/gのものが好ましい。
【００１０】
繊維状活性炭に施す酸化処理としては，硝酸，過マンガン酸塩，次亜塩素酸塩，塩素酸塩，過酸化水素等の酸化剤の高濃度水溶液を用いた液相酸化剤法，及びオゾンを用いた気相酸化剤法等を採用することができる。
【００１１】
酸化処理により繊維状活性炭表面に導入する酸性官能基としては、カルボキシル基、カルボン酸無水物基、フェノール性の水酸基等があり、酸性官能基の量は、官能基に基づく表面酸素濃度が10〜20％となるようにすることが好ましい。酸化処理が進み、酸性官能基が多くなり、表面酸素濃度が20％を超えた繊維状活性炭は、ｐ−アミノアセトアニリドを添着させる表面領域が減少するので、脂肪族アルデヒドの吸着性能を十分に向上させることができない。また、酸化処理が不十分で、酸性官能基が少なく、表面酸素濃度が10％未満の繊維状活性炭は、ｐ−アミノアセトアニリドの再脱離等が生じやすく、脂肪族アルデヒド吸着性能の経時劣化が大きくなる。
本発明において、ｐ−アミノアセトアニリドの添着量は特に限定されるものではないが、繊維状活性炭の重量に対して５〜40％が好ましく、特に20〜30％が好ましい。
【００１２】
酸化処理した繊維状活性炭にｐ−アミノアセトアニリドを添着するに際しては、ｐ−アミノアセトアニリドを、例えばメタノール、エタノール、プロパノール等の低級アルコールに希釈した後、この液に繊維状活性炭を浸漬させ、次いで乾燥させればよいが、ｐ−アミノアセトアニリドの酸化による性能の劣化を避けるため、窒素気流下で乾燥させることが好ましい。
【００１３】
本発明の脂肪族アルデヒド吸着用繊維状活性炭は，原綿状のまま， あるいは単独ないし他の繊維と混合してシート状や円筒状， 円柱状に成形し， これらを収納体内に充填して使用するものである。
【００１４】
【作用】
本発明の脂肪族アルデヒド吸着用繊維状活性炭は、酸化処理により特定比率の酸性官能基を導入した繊維状活性炭にｐ−アミノアセトアニリドを添着したものであるから、ｐ−アミノアセトアニリドの作用により脂肪族アルデヒドに対して優れた吸着性能を有し、吸着した脂肪族アルデヒドの再脱離による空気の汚染もない。
また、理由は明確ではないが、ｐ−アミノアセトアニリドと酸性官能基との相乗作用によって、経時的な性能劣化や洗浄による性能劣化が極めて少ないものである。
【００１５】
【実施例】
次に，本発明を実施例により具体的に説明する。
【００１６】
実施例１，比較例１
燐酸二水素ナトリウム ６００ｇを用いてｐＨを７．０に調整した純水５２リットルに次亜塩素酸ナトリウム１２％水溶液２２００ミリリットルを加え，塩素濃度５０００ｐｐｍ の次亜塩素酸ナトリウム水溶液を調製した。
次いで，この水溶液に比表面積 ９００ｍ２／ｇのピッチ系繊維状活性炭原綿２７０ｇ （温度２２℃，６０％ＲＨで測定） を浸漬し，常温で４５分間撹拌した後，純水により，洗浄，遠心脱水を５回繰り返し，酸化原綿を得た。
さらに，この酸化原綿 ２７０ｇを１．５重量％ｐ−アミノアセトアニリドのメチルアルコール溶液中に常温で３０分間浸漬した後，窒素気流下，常温で１５時間乾燥し，本発明の脂肪族アルデヒド吸着用繊維状活性炭を得た。
【００１７】
このようにして得られた繊維状活性炭（実施例１）と，酸化処理を行わない以外は実施例１と同様にして得られた繊維状活性炭（比較例１）の脂肪族アルデヒド吸着試験を，下記の方法により行った。
【００１８】
アセトアルデヒトの初濃度を２００ｐｐｍに調整したテドラーバック（４リットル）内のガスを，循環ポンプを用いて，繊維状活性炭０．１ｇを入れた直径５ｍｍのガラスカラムに１．３６リットル／分の流量で３０分間循環させた。次いで，アセトアルデヒト検知管により残留濃度を測定し，その除去率を求めた。
また，吸着試験後の繊維状活性炭を，純水中で３０分間撹拌し，乾燥した後，同様の吸着試験と評価を行い，同様の操作を繰り返して５回行った。
評価結果を表１に示す。
【００１９】
【表１】
表１から明らかなように，実施例１の繊維状活性炭は，５回洗浄後も優れた吸着性能を示したが，酸化処理を施さない繊維状活性炭にｐ−アミノアセトアニリドを添着した比較例１のものは，洗浄するたびに吸着性能が低下するものであった。
【００２１】
実施例１と比較例１で得られた脂肪族アルデヒド吸着用繊維状活性炭を用い，空気中の放置日数を変更したものを，上記と同様にして吸着試験を行い，性能を評価した。
評価結果を表２に示す。
【００２２】
【表２】
表２から明らかなように，実施例１の繊維状活性炭は，９０日経過後も優れた吸着性能を示したが，比較例１の繊維状活性炭は，吸着性能が経時的に大幅に低下した。
【００３１】
【発明の効果】
本発明の脂肪族アルデヒド吸着用繊維状活性炭は，脂肪族アルデヒドに対して優れた吸着性能を発揮するだけでなく，再脱離による空気の汚染，経時的な性能劣化及び洗浄による性能劣化が非常に少ないため，非常に広範な用途に利用することができる。さらに，用途に応じて抄紙をはじめとする湿式成形等，各種の成型法で成型することが可能である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a fibrous activated carbon for adsorbing aliphatic aldehyde which is suitable for deodorizing aliphatic aldehyde which is a main cause substance of tobacco odor.
[0002]
[Prior art]
In recent years, offices and personal dwellings have been fully equipped with heat-insulating aluminum sashes, air-conditioning and heating equipment, and soundproofing equipment. It creates various odor problems. One of them is the smell of tobacco in indoor air.
[0003]
The main causative substance of tobacco odor is aliphatic aldehyde. As an aliphatic aldehyde adsorbent, for example, an aromatic primary amine such as aniline impregnated on activated carbon (Japanese Patent Publication No. 60-54095, Japanese Patent Application Laid-Open No. No. 7-136502), a product obtained by impregnating an acidic salt of an aromatic amine with activated carbon (Japanese Patent Application Laid-Open No. 6-225927), a powdered activated carbon comprising a polyalkyleneimine and a nonionic hygroscopic organic substance (eg, polyethylene glycol). (Japanese Patent Publication No. 4-35740) and the like have been proposed.
[0004]
Among the above-mentioned aliphatic aldehyde adsorbents, those using an aromatic amine such as aniline have problems in workability at the time of impregnation, and safety due to indoor contamination due to re-desorption. In addition, those using aromatic amines and polyalkyleneimines deteriorate in their ability to adsorb aliphatic acetaldehyde with time, and once used, washed with water and reused, their ability to adsorb aliphatic acetaldehyde decreases. However, the adsorption effect is not satisfactory. Furthermore, in the wet processing method such as papermaking, since the impregnating substance is dissolved in water and only a substance having low adsorption performance is obtained, there is a disadvantage that the processing method is limited to a specific method.
[0005]
[Problems to be solved by the invention]
The present invention solves the above problems and provides a fibrous activated carbon for adsorbing aliphatic aldehydes, which exhibits excellent performance in aliphatic aldehyde deodorizing applications, and has very little deterioration in performance over time or deterioration due to washing. This is a technical issue.
[0006]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, a fibrous activated carbon having been subjected to a liquid phase oxidation treatment or a gas phase oxidation treatment to introduce a specific ratio of acidic functional groups to the surface thereof has a p-amino acid. It was found that if acetanilide was impregnated, fibrous activated carbon with excellent adsorption performance to aliphatic aldehydes, air pollution due to re-desorption, and less deterioration with time or processing performance could be obtained. The present invention has been reached.
[0007]
That is, the present invention relates to a method for adsorbing aliphatic aldehydes, characterized in that p-aminoacetanilide is impregnated on fibrous activated carbon having a surface oxygen concentration of 10 to 20% into which an acidic functional group has been introduced by oxidation treatment. The main feature is fibrous activated carbon.
In the present invention, the surface oxygen concentration is determined by surface element quantitative analysis by ESCA.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
[0009]
The fibrous activated carbon for aliphatic aldehyde adsorption of the present invention is obtained by impregnating p-aminoacetanilide to an oxidized fibrous activated carbon. Acrylic fiber type, phenol resin (novolak) type, pitch type and the like can be mentioned. Also, the higher the specific surface area of the fibrous activated carbon, the higher the performance can be obtained, but practically preferably 700 to 2000 m 2 / g, the pore diameter is 10 to 30 mm, and the pore volume is 0.25 to 1.30 m 3 / g is preferred.
[0010]
The oxidation treatment applied to the fibrous activated carbon includes a liquid-phase oxidizing method using a high-concentration aqueous solution of an oxidizing agent such as nitric acid, permanganate, hypochlorite, chlorate, hydrogen peroxide, and ozone. The used gas-phase oxidant method or the like can be employed.
[0011]
Examples of the acidic functional group introduced to the fibrous activated carbon surface by the oxidation treatment include a carboxyl group, a carboxylic anhydride group, and a phenolic hydroxyl group.The amount of the acidic functional group is such that the surface oxygen concentration based on the functional group is 10 to It is preferable to make it 20%. Oxidation treatment progresses, the number of acidic functional groups increases, and fibrous activated carbon with a surface oxygen concentration exceeding 20% reduces the surface area to which p-aminoacetanilide is attached, so that the aliphatic aldehyde adsorption performance is sufficiently improved. I can't let it. In addition, fibrous activated carbon having insufficient oxidation treatment, low acidic functional groups, and a surface oxygen concentration of less than 10% is liable to cause the re-desorption of p-aminoacetanilide, etc. growing.
In the present invention, the amount of p-aminoacetanilide impregnated is not particularly limited, but is preferably 5 to 40%, more preferably 20 to 30%, based on the weight of the fibrous activated carbon.
[0012]
When impregnating the oxidized fibrous activated carbon with p-aminoacetanilide, the p-aminoacetanilide is diluted with a lower alcohol such as methanol, ethanol, or propanol, and then the fibrous activated carbon is immersed in the liquid and then dried. However, in order to avoid deterioration in performance due to oxidation of p-aminoacetanilide, it is preferable to dry under a nitrogen stream.
[0013]
The fibrous activated carbon for adsorbing aliphatic aldehydes of the present invention is used as it is, in the form of raw cotton, alone or mixed with other fibers to form a sheet, a cylinder, or a column. Things.
[0014]
[Action]
Since aliphatic aldehyde adsorption fibrous activated carbon of the present invention is obtained by impregnating a p- amino acetanilide fibrous activated carbon has been introduced an acidic functional group of a specific ratio by the oxidation treatment, aliphatic by the action of p- amino acetanilide It has excellent adsorption performance for aldehydes, and there is no air pollution due to redistribution of adsorbed aliphatic aldehydes.
Further, although the reason is not clear, due to the synergistic action of p-aminoacetanilide and the acidic functional group, performance deterioration over time and performance deterioration due to washing are extremely small.
[0015]
【Example】
Next, the present invention will be described specifically with reference to examples.
[0016]
Example 1, Comparative Example 1
To 52 liters of pure water whose pH was adjusted to 7.0 using 600 g of sodium dihydrogen phosphate, 2,200 ml of a 12% aqueous solution of sodium hypochlorite was added to prepare an aqueous solution of sodium hypochlorite having a chlorine concentration of 5000 ppm.
Next, 270 g (measured at a temperature of 22 ° C. and 60% RH) of pitch-based fibrous activated carbon having a specific surface area of 900 m 2 / g is immersed in this aqueous solution, stirred at room temperature for 45 minutes, washed with pure water, and centrifugally dehydrated. Was repeated 5 times to obtain oxidized raw cotton.
Further, 270 g of this oxidized raw cotton was immersed in a 1.5% by weight p-aminoacetanilide methyl alcohol solution at room temperature for 30 minutes, and then dried under a nitrogen stream at room temperature for 15 hours. Activated carbon was obtained.
[0017]
The fibrous activated carbon obtained in this way (Example 1) and the fibrous activated carbon obtained in the same manner as in Example 1 except that the oxidation treatment was not performed (Comparative Example 1) were subjected to an aliphatic aldehyde adsorption test. It carried out by the following method.
[0018]
The gas in a Tedlar bag (4 liters) adjusted to an initial concentration of 200 ppm of acetaldehyde was supplied to a 5 mm diameter glass column containing 0.1 g of fibrous activated carbon at a flow rate of 1.36 liters / minute using a circulation pump. Circulated for 30 minutes. Next, the residual concentration was measured using an acetaldehyde detector tube, and the removal rate was determined.
Further, the fibrous activated carbon after the adsorption test was stirred in pure water for 30 minutes, dried and then subjected to the same adsorption test and evaluation, and the same operation was repeated five times.
Table 1 shows the evaluation results.
[0019]
[Table 1]
As is clear from Table 1, the fibrous activated carbon of Example 1 exhibited excellent adsorption performance even after washing five times, but Comparative Example 1 in which p-aminoacetanilide was impregnated with fibrous activated carbon not subjected to oxidation treatment. In the case of the sample, the adsorption performance was reduced every time washing was performed.
[0021]
Using the fibrous activated carbon for adsorbing aliphatic aldehydes obtained in Example 1 and Comparative Example 1 and changing the number of days of standing in the air, an adsorption test was performed in the same manner as above to evaluate the performance.
Table 2 shows the evaluation results.
[0022]
[Table 2]
As is clear from Table 2, the fibrous activated carbon of Example 1 exhibited excellent adsorption performance even after 90 days, but the adsorption performance of the fibrous activated carbon of Comparative Example 1 was significantly reduced over time.
[0031]
【The invention's effect】
The fibrous activated carbon for adsorbing aliphatic aldehydes of the present invention not only exhibits excellent adsorbing performance for aliphatic aldehydes, but also significantly reduces air contamination due to re-desorption, deterioration over time, and deterioration due to washing. So it can be used for a very wide range of applications. Further, it can be molded by various molding methods such as wet molding including paper making depending on the application.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33150395A JP3571440B2 (en) | 1995-12-20 | 1995-12-20 | Fibrous activated carbon for aliphatic aldehyde adsorption |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33150395A JP3571440B2 (en) | 1995-12-20 | 1995-12-20 | Fibrous activated carbon for aliphatic aldehyde adsorption |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09168736A JPH09168736A (en) | 1997-06-30 |
| JP3571440B2 true JP3571440B2 (en) | 2004-09-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33150395A Expired - Fee Related JP3571440B2 (en) | 1995-12-20 | 1995-12-20 | Fibrous activated carbon for aliphatic aldehyde adsorption |
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| Country | Link |
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| JP (1) | JP3571440B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2013030946A1 (en) * | 2011-08-30 | 2013-03-07 | 富士通株式会社 | Adsorbent and method for producing same |
| JP7103642B2 (en) * | 2018-11-22 | 2022-07-20 | ユニチカ株式会社 | Deodorant and deodorant sheet |
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| Publication number | Publication date |
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| JPH09168736A (en) | 1997-06-30 |
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