JP3173836B2 - Manufacturing method of activated carbon adsorbent - Google Patents
Manufacturing method of activated carbon adsorbentInfo
- Publication number
- JP3173836B2 JP3173836B2 JP35325391A JP35325391A JP3173836B2 JP 3173836 B2 JP3173836 B2 JP 3173836B2 JP 35325391 A JP35325391 A JP 35325391A JP 35325391 A JP35325391 A JP 35325391A JP 3173836 B2 JP3173836 B2 JP 3173836B2
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- Prior art keywords
- activated carbon
- reaction
- amount
- adsorbent
- phenol
- Prior art date
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- Carbon And Carbon Compounds (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、重金属、特に放射性核
種を吸着するのに好適な活性炭吸着材の製造方法に関す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an activated carbon adsorbent suitable for adsorbing heavy metals, especially radionuclides.
【０００２】[0002]
【従来の技術】工場廃液あるいは各種の処理場廃液には
種々の重金属が含まれており、これらの廃液を直接排水
すると河川等の汚染をまねき、環境汚染の問題が生じる
ため、発生源において、蒸発濃縮、イオン交換、凝集沈
澱など種々の方法で除去処理がなされている。2. Description of the Related Art Wastewater from factories or various treatment plants contains various heavy metals, and direct drainage of these wastewaters can lead to pollution of rivers and the like, resulting in environmental pollution. The removal treatment is performed by various methods such as evaporation concentration, ion exchange, and coagulation precipitation.
【０００３】これら重金属の処理方法の中で、イオン交
換樹脂による吸着処理方法は操作性に優れ、作業が簡便
で、処理コストが安価なため、近年一般に採用されてい
る。特に、有害金属のみを選択的に吸着するように特殊
な官能基を有するキレート樹脂の開発が盛んになされ、
現在では、スチレン系あるいはフェノール系を樹脂母体
とした種々のキレート樹脂が使用されている。Among these heavy metal treatment methods, the adsorption treatment method using an ion exchange resin has been generally adopted in recent years because of its excellent operability, simple operation, and low treatment cost. In particular, the development of chelating resins having special functional groups to selectively adsorb only harmful metals has been actively pursued,
At present, various chelate resins based on styrene or phenol resins are used.
【０００４】[0004]
【発明が解決しようとする課題】これらイオン交換樹脂
あるいはキレート樹脂は、高分子骨格に官能基を側鎖と
して共有結合させた樹脂を球状又は繊維状に成形したも
のである。この場合、官能基の導入方法は、一般的に
は、まず球状又は繊維状の高分子骨格を有する樹脂を製
造した後、反応により官能基を導入する方法が採られて
いる。しかしながら、このような反応方法では、官能基
が樹脂内部に入り難く、多くの官能基は樹脂の表面に存
在するようになるため、吸着量を増加するために官能基
量を増加するには、樹脂の比表面積を大きくする必要が
ある。しかるに、比表面積の大きな樹脂あるいは繊維状
成形物は機械的強度が低下し、その増加には限度があっ
た。These ion-exchange resins or chelate resins are obtained by molding a resin in which a functional group is covalently bonded to a polymer skeleton as a side chain into a spherical or fibrous shape. In this case, as a method of introducing a functional group, generally, a method of first producing a resin having a spherical or fibrous polymer skeleton and then introducing a functional group by a reaction is employed. However, in such a reaction method, it is difficult for functional groups to enter the inside of the resin, and many functional groups are present on the surface of the resin. It is necessary to increase the specific surface area of the resin. However, a resin or a fibrous molded product having a large specific surface area has a reduced mechanical strength, and its increase is limited.
【０００５】本発明は、上記の欠点を解消し，吸着材の
強度が強く、官能基量の増加も容易で、しかも、重金属
の吸着性にも優れた活性炭吸着材の製造方法を提供する
ことを技術的な課題とするものである。An object of the present invention is to provide a method for producing an activated carbon adsorbent which solves the above-mentioned drawbacks, has a high strength of the adsorbent, easily increases the amount of functional groups, and is excellent in heavy metal adsorption. Is a technical issue.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、このよう
な課題を解決するために鋭意検討の結果、従来から使用
されている比表面積が広く、機械的性質の優れた吸着材
である活性炭を用い、その表面に、比表面積をできる限
りつぶすことなく、しかも吸着性能の優れた特殊官能基
を多量に添着させれば、吸着性能が優れ、しかも、化学
的、物理的に安定な吸着材を製造できることを知見して
本発明に到達した。Means for Solving the Problems The inventors of the present invention have made intensive studies to solve such problems, and as a result, have found a conventionally used adsorbent having a large specific surface area and excellent mechanical properties. By using activated carbon and adhering a large amount of special functional groups with excellent adsorption performance to the surface without crushing the specific surface area as much as possible, the adsorption performance is excellent and the chemically and physically stable adsorption The inventors have found that a material can be produced, and have reached the present invention.
【０００７】すなわち、本発明は、フェノールとホルマ
リンとを，フェノール１モルに対してホルムアルデヒド
0.05〜１モルとなる割合で濃硫酸溶液中で反応させる工
程と、この反応液に亜燐酸、ホルマリン及び活性炭と、
ジエチレントリアミンを添加、混合し、加温下で反応さ
せる工程からなるアミノメチルホスホン酸系官能基を添
着した活性炭吸着材の製造方法を要旨とするものであ
る。That is, the present invention relates to a method of converting phenol and formalin into formaldehyde per mole of phenol.
A step of reacting in a concentrated sulfuric acid solution at a ratio of 0.05 to 1 mol, and adding phosphorous acid, formalin, and activated carbon to the reaction solution;
The gist of the present invention is a method for producing an activated carbon adsorbent to which an aminomethylphosphonic acid-based functional group is attached, comprising a step of adding, mixing and reacting diethylenetriamine under heating.
【０００８】以下、本発明を詳細に説明する。本発明
は、２段階の工程に別れている。第１段の工程は、フェ
ノールとホルマリンとを，フェノール１モルに対してホ
ルムアルデヒド0.05〜１モルとなる割合で濃硫酸溶液中
で反応させ、メチロール化フェノールを合成する工程で
ある。この反応の特徴は、酸濃度が, 例えば１〜２モル
と非常に高いことである。この様に高い酸濃度を使用す
る理由は、第２段の反応工程において、フェノールとホ
ルムアルデヒドの反応により得られる縮合物が３次元化
することを抑制するためである。第１段の工程の反応温
度は50〜90℃、特に60〜80℃が好ましい。また、反応時
間は１〜２時間が好ましく用いられる。反応終了後は常
温に冷却することがよく、できる限り早く次の工程に供
することが好ましい。なお，ホルムアルデヒドは、ホル
マリンとして使用するのが好ましい。Hereinafter, the present invention will be described in detail. The present invention is divided into two steps. The first step is a step of reacting phenol and formalin in a concentrated sulfuric acid solution at a ratio of 0.05 to 1 mol of formaldehyde to 1 mol of phenol to synthesize methylolated phenol. The characteristic of this reaction is that the acid concentration is very high, for example, 1 to 2 mol. The reason for using such a high acid concentration is to prevent the condensate obtained by the reaction between phenol and formaldehyde from becoming three-dimensional in the second reaction step. The reaction temperature in the first step is preferably from 50 to 90 ° C, particularly preferably from 60 to 80 ° C. The reaction time is preferably 1 to 2 hours. After the completion of the reaction, the reaction is preferably cooled to room temperature, and it is preferable to perform the next step as soon as possible. In addition, it is preferable to use formaldehyde as formalin.
【０００９】本発明の第２段の工程は、第１段の工程で
得た反応物に、亜燐酸、ホルマリン及び活性炭と、ジエ
チレントリアミンを添加、混合し、加温下で反応させる
工程である。[0009] The second stage of the process of the present invention, the reaction product obtained in the first stage of the process, phosphorous acid, and formalin and activated carbon, diethyl
This is a step of adding and mixing tylenetriamine and reacting the mixture under heating.
【００１０】第２段の工程では、好ましくは常温で所定
量の亜燐酸、ホルマリン、水を添加し、十分混合した
後、活性炭を添加する。反応液が活性炭と十分に接触し
た後、ジエチレントリアミンを添加し、混合下で50〜90
℃の温度で１〜４時間反応させる。反応終了後は活性炭
を反応液から分離し、十分洗浄した後、 120〜 130℃で
１〜２時間乾熱処理を行って本発明の活性炭吸着材を得
る。In the second step, preferably, predetermined amounts of phosphorous acid, formalin and water are added at room temperature, and after sufficient mixing, activated carbon is added. After the reaction solution has come into sufficient contact with activated carbon, diethylenetriamine is added and 50-90 under mixing.
The reaction is carried out at a temperature of 1 to 4 hours. After the completion of the reaction, the activated carbon is separated from the reaction solution, sufficiently washed, and then subjected to a dry heat treatment at 120 to 130 ° C. for 1 to 2 hours to obtain the activated carbon adsorbent of the present invention.
【００１１】第２段の工程で使用される亜燐酸の添加量
は得られる反応物中のホスホン基の数に関係し、好まし
い量はフェノール１モルに対して0.５〜1.５モルであ
る。亜燐酸の添加に際しては、あらかじめ水溶液にして
添加する方法も好ましく用いられる。The amount of phosphorous acid used in the second step is related to the number of phosphonic groups in the obtained reaction product, and the preferred amount is 0.5 to 1.5 mol based on 1 mol of phenol. is there. For the addition of phosphorous acid, a method of adding an aqueous solution in advance is also preferably used.
【００１２】また、ジエチレントリアミンの配合量は、
フェノール１モルに対して0.２〜1.５単位モルが好まし
いが、重合度が高いときは含有するアミンの量が、亜燐
酸と等モルであることが好ましい。さらに，ホルマリン
の配合量は、フェノール１モルに対してホルムアルデヒ
ド2.５〜６モルとなる割合が好ましい。The amount of diethylenetriamine is as follows:
The amount is preferably from 0.2 to 1.5 unit mol per mol of phenol, but when the degree of polymerization is high, the amount of amine contained is preferably equimolar to that of phosphorous acid. Further, the compounding amount of formalin is preferably a ratio of 2.5 to 6 mol of formaldehyde to 1 mol of phenol.
【００１３】本発明で使用する活性炭は、粉末、粒状、
繊維状のいずれでもよく、またその原料は木材、椰子
殻、石炭タールピッチ、有機繊維等いずれでもよい。中
でも繊維状活性炭は比表面積が大きいものが製造可能
で、しかもシート、カートリッジ、成形物等に容易に成
形することができるので好ましく用いられる。活性炭の
比表面積は 500〜2500m2／ｇが好ましい、より好ましく
は1500〜2500m2／ｇである。比表面積は大きい方が官能
基の添着量が増大し、有害金属の吸着量も増大するので
好ましい。The activated carbon used in the present invention is powdered, granular,
Any of fibrous materials may be used, and the raw material may be any of wood, coconut shell, coal tar pitch, organic fibers, and the like. Among them, fibrous activated carbon is preferably used because it can be manufactured having a large specific surface area and can be easily formed into sheets, cartridges, molded products and the like. The specific surface area of activated carbon 500~2500m 2 / g is preferred, more preferably 1500~2500m 2 / g. It is preferable that the specific surface area is large because the amount of functional group attached increases and the amount of harmful metal adsorbed increases.
【００１４】第２段の工程における活性炭と添加物との
混合比率は、活性炭１kgに対して、フェノールで0.６〜
20モル、好ましくは0.６〜10モルの範囲であり、他成分
の混合比率は上記条件で調整した量である。The mixing ratio of activated carbon and additives in the second stage is 0.6 to phenol per 1 kg of activated carbon.
The amount is 20 mol, preferably 0.6 to 10 mol, and the mixing ratio of the other components is an amount adjusted under the above conditions.
【００１５】第２段の工程で、活性炭をカラムに充填
し、反応液を循環させて連続的に反応させる方法を採る
場合は水を特別に添加する必要はなく，例えばホルマリ
ンに含まれる水だけでよいが、上記以外の方法で反応さ
せる場合は、活性炭の種類により添加する水の量を調整
する。ここで使用する水の量は少ない方がよく、活性炭
が反応液と接触できる最低量でよい。In the second step, when a method is used in which activated carbon is packed in a column and the reaction solution is circulated to continuously react, there is no need to add water, for example, only water contained in formalin. However, when the reaction is performed by a method other than the above, the amount of water to be added is adjusted depending on the type of activated carbon. The amount of water used here is preferably as small as possible, and may be the minimum amount at which the activated carbon can contact the reaction solution.
【００１６】本発明における反応は、バッチ法、連続法
の何れで行ってもよく、特に限定されるものではない。
バッチ法の場合の添加順序は、第１段の工程の反応にお
いては、フェノールに対して先ず濃硫酸、次いでホルマ
リンを添加することが好ましく、また添加時の温度は50
℃を超えないようにすることが好ましい。次に、第２段
の工程の反応においては、反応生成物に対し、亜燐酸水
溶液、ホルマリン、水、活性炭、ジエチレントリアミン
の順で添加することが好ましいが、これに限定されるも
のではない。The reaction in the present invention may be carried out by any of a batch method and a continuous method, and is not particularly limited.
In the case of the batch method, it is preferable to add concentrated sulfuric acid and then formalin to phenol in the reaction of the first step in the reaction of the first step, and the temperature at the time of addition is 50%.
It is preferred that the temperature is not exceeded. Next, in the reaction of the second step, it is preferable to add an aqueous solution of phosphorous acid, formalin, water, activated carbon, and diethylenetriamine to the reaction product in this order, but it is not limited thereto. is not.
【００１７】また、第１段の工程の反応をバッチ式に
し、第２段の工程はカラム法を採用することが特に好ま
しい。カラム法の場合は、活性炭をカラムに充填し、こ
こに活性炭以外の反応物を混合した液を連続的に流通さ
せ、活性炭に接触させて反応させる方法が好ましいが、
これに限定されるものではない。It is particularly preferable that the reaction in the first step is a batch process and that the second step is a column method. In the case of the column method, a method in which activated carbon is packed in a column and a liquid in which a reactant other than activated carbon is mixed is continuously passed through the column and the activated carbon is brought into contact with the activated carbon to perform a reaction,
It is not limited to this.
【００１８】本発明で得られる活性炭吸着材は、活性炭
の表面に、その比表面積をできるだけ減じることなく、
重金属に対して特異的な吸着性を有するアミノメチルホ
スホン酸系の官能基を添着したものである。このため、
従来の吸着材は比表面積が最大のものでも 500m2／ｇを
超えるものがないのに対し、本発明では、原料となる活
性炭にもよるが、 500m2／ｇ以上の活性炭吸着材を容易
に得ることができる。このため、本発明で得られる活性
炭吸着材は、吸着速度の向上と同時に、従来の吸着材で
は困難であった、わずかの選択性の異なる物質を容易に
カラム法で分別できるものであり、ウラン、プルトニウ
ム等の放射性金属に対しても優れた選択吸着性を有す
る。The activated carbon adsorbent obtained by the present invention can be used on the surface of activated carbon without reducing its specific surface area as much as possible.
An aminomethylphosphonic acid-based functional group having specific adsorptivity to heavy metals is attached. For this reason,
While the conventional adsorbent has no specific surface area of at most 500 m 2 / g, in the present invention, an activated carbon adsorbent of 500 m 2 / g or more can be easily prepared depending on the activated carbon used as a raw material. Obtainable. For this reason, the activated carbon adsorbent obtained by the present invention is capable of improving the adsorption rate and simultaneously separating substances having slightly different selectivities, which were difficult with the conventional adsorbent, by the column method. It also has excellent selective adsorption to radioactive metals such as plutonium.
【００１９】[0019]
【実施例】次に、本発明を実施例によって具体的に説明
する。Next, the present invention will be described specifically with reference to examples.
【００２０】実施例１ ５リツトルの硝子製ビーカーにフェノール94ｇを採取
し, フェノールの温度を50℃以下に保ちながら98％濃硫
酸 170ｇを攪拌しながら徐々に添加した。次に、37％ホ
ルマリン９mlを同様に添加した後、液温を70℃に上げて
１時間反応させ、その後ただちに常温に冷却した。この
液に亜燐酸70ｇと水25ｇの混合物を攪拌しながら添加
し、次に、37％ホルマリン 300mlを同様に添加した。こ
の混合液に、椰子殻活性炭（粒状、20〜40メッシュ、比
表面積約900m2/ｇ）100 ｇを添加した後、水を活性炭が
完全に反応液と接触するようになる量（約 200ml）添加
し、さらにジエチレントリアミン40mlを添加した。この
液の温度を80℃にして３時間反応させ、終了後直ちに反
応液を分離し、活性炭を十分水洗した。水洗後、 125℃
で1.５時間乾熱処理して本発明の活性炭吸着材 132ｇを
得た。また、この活性炭吸着材の燐添着量は4.９ｇ／k
g、比表面積は 650m2／ｇであった。Example 1 In a 5-liter glass beaker, 94 g of phenol was collected, and 170 g of 98% concentrated sulfuric acid was gradually added while stirring the phenol at a temperature of 50 ° C. or lower. Next, 9 ml of 37% formalin was added in the same manner, the liquid temperature was raised to 70 ° C., and the reaction was carried out for 1 hour, and then immediately cooled to room temperature. To this solution, a mixture of 70 g of phosphorous acid and 25 g of water was added with stirring, and then 300 ml of 37% formalin was similarly added. 100 g of coconut shell activated carbon (granular, 20 to 40 mesh, specific surface area of about 900 m 2 / g) is added to the mixture, and water is added to the mixture so that the activated carbon completely comes into contact with the reaction solution (about 200 ml). And then 40 ml of diethylenetriamine. The temperature of the solution was raised to 80 ° C., and the reaction was carried out for 3 hours. After washing with water, 125 ℃
For 1.5 hours to obtain 132 g of the activated carbon adsorbent of the present invention. The amount of phosphorus impregnated in this activated carbon adsorbent is 4.9 g / k.
g and specific surface area were 650 m 2 / g.
【００２１】この吸着材１ｇをＣｅ3+濃度4.87mg／l の
Ｃｅ（ＮＯ3)3 100ml中に添加し、吸着させた。その結
果、Ｃｅ吸着量は0.40mg／ｇ（吸着率82％）であった。1 g of this adsorbent was added to 100 ml of Ce (NO 3 ) 3 having a Ce 3+ concentration of 4.87 mg / l, and adsorbed. As a result, the Ce adsorption amount was 0.40 mg / g (adsorption rate 82%).
【００２２】比較のため、原料の椰子殻活性炭をそのま
ま使用して同様の条件で吸着させたが、Ｃｅ吸着量は0.
03mg／ｇ（吸着率６％）にすぎなかった。For comparison, coconut shell activated carbon as a raw material was used as it was and adsorbed under the same conditions, but the Ce adsorption amount was 0.
It was only 03 mg / g (adsorption rate 6%).
【００２３】実施例２ ５リットルの硝子製ビーカーに、実施例１と同一の条件
で製造した第１工程の反応液72ｇを採取し、これに亜燐
酸17.4ｇ、水6.２ｇ、37％ホルマリン74mlの順に常温で
攪拌しながら添加した。この液を、さらに水 300mlで希
釈した後、繊維状活性炭（ユニチカ社製Ａ−２０：比表
面積2116m2／ｇ）30ｇを添加して十分反応液と接触さ
せ、直ちにジエチレントリアミン9.９mlを添加した。こ
の液の温度を80℃とし３時間反応させた後、残液を分離
除去した。さらに水洗した後、反応物を 100℃で1.５時
間乾熱処理して本発明の活性炭吸着材56ｇを得た。ま
た、この活性炭吸着材の燐添着量は10.3ｇ／kg、比表面
積は1014m2／ｇであった。Example 2 In a 5-liter glass beaker, 72 g of the reaction solution of the first step produced under the same conditions as in Example 1 was collected, and 17.4 g of phosphorous acid, 6.2 g of water, and 37% formalin were added. It was added in the order of 74 ml while stirring at room temperature. After further diluting this solution with 300 ml of water, 30 g of fibrous activated carbon (A-20 manufactured by Unitika Ltd .: specific surface area of 2116 m 2 / g) was added thereto, sufficiently brought into contact with the reaction solution, and 9.9 ml of diethylenetriamine was immediately added. . After the temperature of the liquid was raised to 80 ° C. and the reaction was carried out for 3 hours, the remaining liquid was separated and removed. After further washing with water, the reaction product was subjected to a dry heat treatment at 100 ° C. for 1.5 hours to obtain 56 g of the activated carbon adsorbent of the present invention. The activated carbon adsorbent had a phosphorus impregnation amount of 10.3 g / kg and a specific surface area of 1014 m 2 / g.
【００２４】この吸着材１ｇをＣｅ3+濃度4.86mg／l の
Ｃｅ（ＮＯ3)3 100ml中に添加し、吸着させた。その結
果、Ｃｅ吸着量は0.48mg／ｇ（吸着率99％）であった。1 g of this adsorbent was added to 100 ml of Ce (NO 3 ) 3 having a Ce 3+ concentration of 4.86 mg / l, and adsorbed. As a result, the Ce adsorption amount was 0.48 mg / g (adsorption rate: 99%).
【００２５】比較のため、原料の繊維状活性炭（Ａ−２
０）をそのまま使用して同様の条件で吸着させたが、Ｃ
ｅ吸着量は0.026mg ／ｇ（吸着率５％）にすぎなかっ
た。For comparison, the raw material fibrous activated carbon (A-2)
0) was used as it was and adsorbed under the same conditions.
e The amount of adsorption was only 0.026 mg / g (adsorption rate 5%).
【００２６】実施例３ 実施例２で得られた活性炭吸着材10ｇを，内径14.8mm,
高さ 500mmのガラス製カラムに充填し, カートリッジを
作成した。このカートリツジに, Ｃｅ3+濃度２mg／l ，
Ｃａ2+濃度 100mg／l ，Ｎａ+ 濃度 10g／l の溶液を２
リットル通液して吸着させた。その結果、吸着率は，Ｃ
ｅ3+が100 ％, Ｃａ2+が１％，Ｎａ+ が０％であり，高
い選択吸着性を示した。Example 3 10 g of the activated carbon adsorbent obtained in Example 2 was
A 500 mm high glass column was packed to make a cartridge. In this cartridge, Ce 3+ concentration 2mg / l,
A solution having a Ca 2+ concentration of 100 mg / l and a Na + concentration of 10 g / l
One liter of the solution was adsorbed. As a result, the adsorption rate becomes C
e 3+ was 100%, Ca 2+ was 1%, and Na + was 0%, indicating high selective adsorption.
【００２７】[0027]
【発明の効果】本発明によれば、吸着材の強度が強く、
官能基量の増加も容易で、しかも、重金属の吸着性にも
優れた活性炭吸着材を容易に安定して製造することが可
能となる。According to the present invention, the strength of the adsorbent is high,
It is possible to easily and stably produce an activated carbon adsorbent which is easy to increase in the amount of functional groups and also excellent in heavy metal adsorption.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 木崎 文彦 大阪府泉南郡熊取町野田644−33 (56)参考文献 特開 平５−164896（ＪＰ，Ａ) 特開 平２−290824（ＪＰ，Ａ) 特開 昭58−186436（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 20/00 - 20/34 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Fumihiko Kizaki 644-33 Noda, Kumatori-cho, Sennan-gun, Osaka (56) References JP-A-5-164896 (JP, A) JP-A-2-290824 (JP, A) JP-A-58-186436 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) B01J 20/00-20/34
Claims (2)
ル１モルに対してホルムアルデヒド0.05〜１モルとなる
割合で濃硫酸溶液中で反応させる工程と、この反応液に
亜燐酸、ホルマリン及び活性炭と、ジエチレントリアミ
ンを添加、混合し、加温下で反応させる工程からなるア
ミノメチルホスホン酸系官能基を添着した活性炭吸着材
の製造方法。1. A step of reacting phenol and formalin in a concentrated sulfuric acid solution at a ratio of 0.05 to 1 mol of formaldehyde with respect to 1 mol of phenol, and adding phosphoric acid, formalin and activated carbon, diethylenetriamine
A method for producing an activated carbon adsorbent to which an aminomethylphosphonic acid functional group is attached, comprising a step of adding, mixing and reacting under heating.
載の活性炭吸着材の製造方法。2. The method for producing an activated carbon adsorbent according to claim 1, wherein the activated carbon is fibrous activated carbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35325391A JP3173836B2 (en) | 1991-12-17 | 1991-12-17 | Manufacturing method of activated carbon adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35325391A JP3173836B2 (en) | 1991-12-17 | 1991-12-17 | Manufacturing method of activated carbon adsorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05168917A JPH05168917A (en) | 1993-07-02 |
| JP3173836B2 true JP3173836B2 (en) | 2001-06-04 |
Family
ID=18429590
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35325391A Expired - Lifetime JP3173836B2 (en) | 1991-12-17 | 1991-12-17 | Manufacturing method of activated carbon adsorbent |
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| Country | Link |
|---|---|
| JP (1) | JP3173836B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108940223A (en) * | 2018-08-04 | 2018-12-07 | 安徽科浦环保科技有限公司 | A kind of preparation method of the compound scavenger of indoor formaldehyde |
| CN114849664B (en) * | 2022-04-20 | 2023-09-29 | 齐鲁工业大学 | Phosphorous acid modified polyphenol amine adsorption material and preparation method and application thereof |
| WO2024204684A1 (en) * | 2023-03-30 | 2024-10-03 | 三井金属鉱業株式会社 | Porous body, adsorptive material containing porous body, and method for removing metal and/or metal ion using adsorptive material |
-
1991
- 1991-12-17 JP JP35325391A patent/JP3173836B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JPH05168917A (en) | 1993-07-02 |
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