JP3516811B2 - Activated carbon fiber molded adsorbent - Google Patents
Activated carbon fiber molded adsorbentInfo
- Publication number
- JP3516811B2 JP3516811B2 JP18418696A JP18418696A JP3516811B2 JP 3516811 B2 JP3516811 B2 JP 3516811B2 JP 18418696 A JP18418696 A JP 18418696A JP 18418696 A JP18418696 A JP 18418696A JP 3516811 B2 JP3516811 B2 JP 3516811B2
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- adsorbent
- carbon fiber
- fibers
- molded
- 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
Links
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
- Separation Of Gases By Adsorption (AREA)
Description
【0001】[0001]
【発明の属する技術分野】本発明は活性炭繊維成形吸着
体に関するもので更に詳しく述べると、活性炭繊維のト
ウにフィブリル化した耐アルカリ性セルローズ繊維を混
合・包絡して得られた成形体で、気相或いは液相中に含
まれる着色物質、悪臭物質その他の有害物質等を吸着除
去するために使用される成形吸着体である。TECHNICAL FIELD The present invention relates to an activated carbon fiber molded adsorbent, and more specifically, it is a molded body obtained by mixing and encapsulating fibrillated alkali-resistant cellulose fibers with a tow of activated carbon fibers, which has a gas phase Alternatively, it is a molded adsorbent used for adsorbing and removing coloring substances, malodorous substances and other harmful substances contained in the liquid phase.
【0002】[0002]
【従来の技術】活性炭繊維は従来から使用されている粒
状活性炭に較べて比表面積が大きく吸脱着速度が速いた
め、織物、マット、フエルト状等に加工して溶剤回収装
置やエアークリーナー等の気相中で使用する吸着材や、
浄水器用フィルター等の液相中で使用する吸着材として
使用されている。しかし、活性炭繊維は充填密度が低く
更に機械的強度が乏しいために、これを原料として作成
された脱臭フィルター等は機械的強度が乏しく、充填密
度が低いというデメリットが避けられなかった。BACKGROUND OF THE INVENTION Activated carbon fiber has a large specific surface area and a high adsorption / desorption rate compared to conventionally used granular activated carbon. Therefore, it is processed into fabrics, mats, felts, etc., and used in solvent recovery equipment and air cleaners. The adsorbent used in the phase,
It is used as an adsorbent used in the liquid phase of filters for water purifiers. However, since activated carbon fiber has a low packing density and further poor mechanical strength, deodorizing filters and the like made from this material have poor mechanical strength and the disadvantage that packing density is low is unavoidable.
【0003】活性炭繊維を使用した成形吸着体は活性炭
繊維の弱点である、機械的強度及び充填密度を改善する
ために開発されたもので、今迄に開示されている主な活
性炭繊維を使用した成形体には次の様なものがある。A molded adsorbent using activated carbon fibers was developed to improve mechanical strength and packing density, which are weak points of activated carbon fibers, and the main activated carbon fibers disclosed so far have been used. There are the following molded products.
【0004】(1)活性炭繊維及び熱溶融性合成樹脂を
含み、活性炭繊維が熱溶融性合成樹脂によりランダムに
接合保持され、一体的に成形された抄紙構造を有する成
形吸着体(特公平 5-55183号、特公平 7-12429号公報)
である。熱溶融性合成樹脂としては融点が50〜200 ℃の
ポリマーが使用されている。具体的にはポリエチレン、
ポリプロピレン、ポリビニルアルコール、ポリアクリロ
ニトリル等である。(1) A shaped adsorbent containing activated carbon fibers and a heat-meltable synthetic resin, in which the activated carbon fibers are randomly bonded and held by the heat-meltable synthetic resin and integrally formed to have a papermaking structure (Japanese Patent Publication No. 5- (55183, Japanese Patent Publication No. 7-12429)
Is. As the heat-meltable synthetic resin, a polymer having a melting point of 50 to 200 ° C. is used. Specifically, polyethylene,
Examples thereof include polypropylene, polyvinyl alcohol, polyacrylonitrile and the like.
【0005】この方法によれば密度の高い成形吸着体を
得ることができるが、成形体の強度が弱く且つ成形体の
耐熱性が低いという問題点があった。活性炭繊維は 100
℃以上の温度で再生すれば繰り返し使用可能であるが、
バインダーとして熱溶融性樹脂を使用した場合には加熱
時の強度が極端に低下して変形するおそれがあるため、
充分に再生することが困難となる問題点があった。ま
た、熱溶融性樹脂をバインダーとして成形する場合に
は、熱溶融性合成樹脂との混合スラリーから吸引成型し
脱水後加熱乾燥して成型体を作成する。しかし、吸引成
形して得られた成形体の強度が低いため、成形用の型枠
からの成形体の取り出しが難しくまた無理に取り出すと
成形体が変形するおそれがあった。このため成形体の収
率が低下する問題点もあった。According to this method, a molded adsorbent having a high density can be obtained, but there is a problem that the strength of the molded body is weak and the heat resistance of the molded body is low. 100 activated carbon fibers
It can be used repeatedly if it is regenerated at a temperature above ℃,
When a heat-meltable resin is used as the binder, the strength during heating may extremely decrease and deform,
There has been a problem that it is difficult to reproduce it sufficiently. When the heat-meltable resin is used as a binder, it is suction-molded from a mixed slurry with the heat-meltable synthetic resin, dehydrated, and then heat-dried to form a molded body. However, since the strength of the molded product obtained by suction molding is low, it is difficult to take out the molded product from the molding frame, and if it is forcibly taken out, the molded product may be deformed. For this reason, there is also a problem that the yield of the molded product decreases.
【0006】(2)活性炭を主成分とする成形吸着体に
おいて、フィブリル化されたアラミド繊維或いはフィブ
リル化されたアクリル繊維を包絡材として、この絡み合
いで活性炭を結合させた成形吸着体が開示されている
(特開平 6-335632 号、特開平7-16458 号公報) 。この
吸着成形体は耐熱性が高い特徴がありまたフィブリル化
された包絡材を使用することにより、前記成形体に較べ
て強度面でも大幅に改善されている。また、成形体の湿
式強度も高いために型枠から取り出す場合に成形体が型
くずれする問題も大幅に改善されている。しかし、実用
的観点からは尚この成形吸着体は充分な強度を持ってい
ない。(2) In a shaped adsorbent containing activated carbon as a main component, a shaped adsorbent in which fibrillated aramid fibers or fibrillated acrylic fibers are used as an enveloping material and activated carbon is bound by this entanglement is disclosed. (JP-A-6-335632 and JP-A-7-16458). This adsorption molded body has a characteristic of high heat resistance, and by using a fibrillated envelope material, the strength is significantly improved as compared with the molded body. In addition, since the wet strength of the molded product is high, the problem that the molded product loses its shape when taken out from the mold has been greatly improved. However, from a practical point of view, this molded adsorbent still does not have sufficient strength.
【0007】上記の吸着成形体は活性炭繊維とバインダ
ーとの混合スラリーを作り、このスラリーを吸引成形、
脱水、乾燥することにより作成されるものである。この
方法とは対照的な乾式で成形吸着体を得る方法も開示さ
れている。[0007] The above-mentioned adsorption molded body makes a mixed slurry of activated carbon fibers and a binder, and suction-molds this slurry.
It is created by dehydration and drying. In contrast to this method, a method for obtaining a shaped adsorbent by a dry method is also disclosed.
【0008】(3)活性炭繊維と熱溶融合成樹脂繊維と
を混紡または混合した後加熱して両者を融着させた成形
吸着体が開示されている(特開昭56-24151号公報) 。し
かし、この方法では複雑な構造の成形吸着体をつくるこ
とができないため、この成形吸着体は充分な実用性を持
っていなかった。(3) A molded adsorbent in which activated carbon fibers and hot-melt synthetic resin fibers are mixed or mixed and then heated to fuse the two is disclosed (JP-A-56-24151). However, since this method cannot produce a shaped adsorbent having a complicated structure, this shaped adsorbent has not been sufficiently practical.
【0009】[0009]
【発明が解決しようとする課題】前述の様に従来の活性
炭繊維を主体とする成形吸着体の有する問題点である、
耐熱性、成形体の強度或いは複雑な構造の成型等が不十
分であることを考慮して、耐熱性及び強度が高く更に成
形性も優れた活性炭繊維成形吸着体を開発して提供しよ
うとするものである。As described above, there are problems with the conventional molded adsorbent mainly composed of activated carbon fiber,
Considering that heat resistance, strength of molded body or molding of complicated structure is insufficient, we will develop and provide activated carbon fiber molded adsorbent with high heat resistance and strength and excellent moldability. It is a thing.
【0010】[0010]
【課題を解決するための手段】活性炭繊維は優れた吸着
特性を有するが機械的強度が弱く、また充填密度が低い
性質を改善して機械的強度及び充填密度が高く、更に耐
熱性及び成形性も優れ圧損失も低い立体構造を持つ成形
吸着体を形成させるため、この目的に適合する包絡材に
ついて研究した。その結果、耐アルカリ性を有するフィ
ブリル化セルローズ繊維がこの目的に好適なことを見出
し、これに基づいて本発明に到達した。[Means for Solving the Problems] Activated carbon fibers have excellent adsorption properties, but have weak mechanical strength and low packing density, which improves the mechanical strength and packing density, as well as heat resistance and moldability. In order to form a molded adsorbent having a three-dimensional structure with excellent pressure loss and low pressure loss, an envelope material suitable for this purpose was studied. As a result, they have found that fibrillated cellulose fibers having alkali resistance are suitable for this purpose, and have reached the present invention based on this.
【0011】すなわち、主成分として活性炭繊維及び包
絡材としてフィブリル化した耐アルカリ性セルローズ繊
維を含む活性炭繊維成形吸着体である。ここで、セルロ
ーズ繊維としてはポリノジックレーヨン繊維或いは、マ
ーセル化天然セルローズ繊維が好ましい。また本発明の
成形体において、フィブリル化した耐アルカリ性セルロ
ーズ繊維の含有量が活性炭繊維 100重量部に対して、0.
3 〜20重量部である成形吸着体が好ましい。That is, it is an activated carbon fiber molded adsorbent containing activated carbon fibers as a main component and fibrillated alkali resistant cellulose fibers as an enveloping material. Here, as the cellulose fibers, polynosic rayon fibers or mercerized natural cellulose fibers are preferable. Further, in the molded product of the present invention, the content of the fibrillated alkali-resistant cellulose fiber is 0.
Molded adsorbents of 3 to 20 parts by weight are preferred.
【0012】尚、本発明の成形吸着体はアルカリ溶液中
で使用することはないが、包絡材の性能の指標としてセ
ルローズ繊維の耐アルカリ性を選択したのは、得られた
成形体の性能と包絡材として使用したセルローズ繊維の
耐アルカリ性の間に、見掛上高い相関関係があることを
見出したからである。以下、本発明について詳しく説明
する。Although the molded adsorbent of the present invention is not used in an alkaline solution, the alkali resistance of the cellulosic fiber was selected as an index of the performance of the envelope material because the performance and the envelope of the obtained molded body were selected. This is because it was found that there is an apparently high correlation between the alkali resistance of the cellulose fibers used as the material. Hereinafter, the present invention will be described in detail.
【0013】本発明の成形吸着体の主成分は活性炭繊維
である。ここで使用される活性炭繊維は特に限定されず
通常1gあたり数100 m2或いはそれ以上の大きな比表面積
を有し、高い吸着性を示す繊維状炭素材料であれば広範
囲に使用できる。これらの中本発明には直径2〜20μm
、比表面積 500〜3000m2/g、細孔半径3〜20Åの活性
炭繊維が好ましい。The main component of the shaped adsorbent of the present invention is activated carbon fiber. The activated carbon fiber used here is not particularly limited, and generally has a large specific surface area of several 100 m 2 or more per 1 g, and can be used in a wide range as long as it is a fibrous carbon material exhibiting high adsorptivity. Among these, the present invention has a diameter of 2 to 20 μm.
, Activated carbon fibers having a specific surface area of 500 to 3000 m 2 / g and a pore radius of 3 to 20 Å are preferable.
【0014】活性炭繊維の原料も特に限定されない。例
えば、レーヨン系、ポリアクリロニトリル系、フェノー
ル樹脂系、石油ピッチ系、石炭ピッチ系等いずれの繊維
も原料として使用可能である。本発明においては活性炭
繊維の他に粒状活性炭、粉末活性炭、ゼオライト等の吸
着剤を混合し、更に包絡材を加えて成形してもよい。活
性炭繊維に対する他の材料の混合割合は特に限定されな
いが、成形吸着体に占める活性炭繊維の体積割合が50%
以下になった場合には活性炭繊維の吸着性能の優越性が
発揮できない。The raw material of the activated carbon fiber is also not particularly limited. For example, rayon fibers, polyacrylonitrile fibers, phenol resin fibers, petroleum pitch fibers, coal pitch fibers and the like can all be used as raw materials. In the present invention, an adsorbent such as granular activated carbon, powdered activated carbon, or zeolite may be mixed in addition to the activated carbon fiber, and an envelope material may be further added to perform molding. The mixing ratio of other materials to the activated carbon fiber is not particularly limited, but the volume ratio of the activated carbon fiber in the molded adsorbent is 50%.
When it becomes below, the superiority of the adsorption performance of the activated carbon fiber cannot be exhibited.
【0015】本発明の成形吸着体において、活性炭繊維
の充填密度は0.12〜0.25 g/cc であるが、粒状の吸着材
の密度は活性炭繊維の密度より一般にかなり高い(例え
ば粒状活性炭の場合充填密度は0.4 g/cc程度)。粒状活
性炭を70重量%程度混合した場合に体積割合において活
性炭繊維と粒状活性炭とがほぼ同等の割合になる。In the shaped adsorbent of the present invention, the packing density of activated carbon fibers is 0.12 to 0.25 g / cc, but the density of the granular adsorbent is generally much higher than that of the activated carbon fibers (for example, in the case of granular activated carbon, the packing density is Is about 0.4 g / cc). When about 70% by weight of granular activated carbon is mixed, the activated carbon fibers and the granular activated carbon have almost the same volume ratio.
【0016】本発明の活性炭繊維成形吸着体には活性炭
繊維以外の主成分として、フィブリル化した耐アルカリ
性セルローズ繊維が含まれている。ここで使用される耐
アルカリ性セルローズ繊維は特に限定されないが、例え
ば、ポリノジックレーヨン繊維及びマーセル化した天然
セルローズ繊維等である。ポリノジックレーヨン繊維は
セルローズキサントゲン酸ソーダを凝固性が低い紡糸浴
中に押し出して、延伸しながら徐々に凝固させて得られ
たもので、繊維の断面形状が円形で表面も平滑である。
また繊維はミクロフィブリル構造を有するためフィブリ
ル化し易く、重合度は 400以上で通常レーヨンよりかな
り高く、吸水性が低く湿潤強度も高い特徴がある。The activated carbon fiber molded adsorbent of the present invention contains fibrillated alkali resistant cellulose fibers as a main component other than the activated carbon fibers. The alkali-resistant cellulose fibers used here are not particularly limited, and examples thereof include polynosic rayon fibers and mercerized natural cellulose fibers. The polynosic rayon fiber is obtained by extruding sodium cellulose xanthate into a spinning bath having a low coagulability and gradually coagulating while stretching, and the fiber has a circular cross-sectional shape and a smooth surface.
Further, the fibers have a microfibril structure and are easily fibrillated. The degree of polymerization is 400 or more, which is considerably higher than that of ordinary rayon, and the water absorption is low and the wet strength is high.
【0017】マーセル化処理とは針葉樹木材パルプ、広
葉樹木材パルプ、パイナップルパルプ、マニラ麻パルプ
及びサイザル麻パルプ等の天然セルローズ繊維を冷アル
カリ、例えば40%程度の水酸化カリウム溶液中に3〜4
時間浸漬して繊維を膨潤させ、パルプ中の崩壊し易いヘ
ミセルロースを除去すると同時に偏平であった繊維の断
面を円形化したものである。またリンターパルプなどの
α−セルロース含有率が高いパルプを原料とした再生セ
ルロース繊維、例えばポリノジックレーヨンは本来耐ア
ルカリ性が高く、また叩解することにより容易にフィブ
リル化するので本発明の包絡材に適している。What is the mercerization treatment? Natural cellulose fibers such as softwood wood pulp, hardwood wood pulp, pineapple pulp, Manila hemp pulp and sisal pulp are placed in a cold alkali, for example, 3 to 4 in a 40% potassium hydroxide solution.
The fibers are swollen by immersing for a period of time to remove hemicellulose, which easily disintegrates in the pulp, and at the same time, the flat cross section of the fibers is circularized. Further, regenerated cellulose fibers made of pulp having a high α-cellulose content such as linter pulp, for example, polynosic rayon, are originally high in alkali resistance and easily fibrillated by beating, and thus are suitable for the envelope material of the present invention. There is.
【0018】本発明においてフィブリル化された耐アル
カリ性セルローズ繊維は水中で活性炭繊維と攪拌・混合
されて、水性スラリーが調整され活性炭繊維はフィブリ
ル化セルローズ繊維で包絡された状態となっている。更
にスラリーは多数の吸引用小穴を有する成形用の型枠を
通して濾過されて、フィブリル化セルローズ繊維で包絡
された活性炭繊維成形吸着体が成形され、脱水後加熱乾
燥することにより本発明の成形吸着体が得られる。In the present invention, the fibrillated alkali-resistant cellulose fibers are stirred and mixed with the activated carbon fibers in water to prepare an aqueous slurry, and the activated carbon fibers are in a state of being enveloped with the fibrillated cellulose fibers. Further, the slurry is filtered through a mold for molding having a large number of small holes for suction to form an activated carbon fiber molded adsorbent enveloped with fibrillated cellulose fibers, which is dehydrated and dried by heating to form the molded adsorbent of the present invention. Is obtained.
【0019】耐アルカリ性が低いセルロース繊維を成形
吸着体の包絡材に使用した場合には成形吸着体の圧力損
失が増大する現象が認められる。圧力損失は一定量の流
体を流す場合に必要となる圧力をいう。成形吸着体は主
として液体および気体を通過させ、この液体および気体
に含まれる悪臭物質等不純物を除去するために使用され
るが、圧力損失が低い程一定の圧力で多量の流体を流す
ことができるため好ましい。When cellulosic fibers having low alkali resistance are used as the envelope material of the molded adsorbent, a phenomenon in which the pressure loss of the molded adsorbent increases is observed. Pressure loss refers to the pressure required to flow a certain amount of fluid. The shaped adsorbent is mainly used to pass liquids and gases and remove impurities such as malodorous substances contained in the liquids and gases. The lower the pressure loss, the more fluid can flow at a constant pressure. Therefore, it is preferable.
【0020】通常の天然繊維を叩解して得られたフィブ
リルを包絡材として使用した場合には圧力損失の増大が
認められた。これに対して、耐アルカリ性を有するセル
ロース繊維を叩解して得られたフィブリルを包絡材に使
用した場合には圧力損失の増加は殆どなかった。この理
由は天然繊維を叩解したパルプは繊維の断面形状が偏平
状であるのに対し、耐アルカリ性セルロース繊維を叩解
したフィブリルの断面は円形に近いためであることに起
因すると考えられる。When fibrils obtained by beating ordinary natural fibers were used as an envelope material, an increase in pressure loss was observed. On the other hand, when fibrils obtained by beating cellulose fibers having alkali resistance were used as the envelope material, there was almost no increase in pressure loss. The reason for this is considered to be that the pulp that is beaten with natural fibers has a flat cross-section, whereas the fibrils that have been beaten with alkali-resistant cellulose fibers have a cross-section close to a circle.
【0021】前記の様に耐アルカリ性を有するセルロー
ス繊維を叩解して得られたフィブリルを包絡材に使用し
た場合には、成型吸着体の圧力損失の増加が抑制される
ことが認められるが、それにも拘らず成型吸着体の機械
的強度及び複雑な形状に成型することを可能とする成型
性向上の効果も認められる。これはフィブリル化したポ
リノジックレーヨン繊維またはマーセル化天然セルロー
ズ繊維の形状が、長い幹から多くの短い枝が生えた様な
形状を有するため、活性炭繊維を包絡した場合その構造
性を強化する機能が高いのに対して、天然繊維をそのま
ま叩解して得られたフィブリルは太く短い枝が不規則に
集積した様なバラバラな形状で存在するため、活性炭繊
維を包絡してもその構造性を強化する機能が乏しいため
と考えられる。本発明者等の試験の結果前述の様なフィ
ブリルの包絡機能を表示するパラメーターとしては、セ
ルロース繊維の耐アルカリ性が見掛上最も優れているこ
とが認められた。When fibrils obtained by beating cellulosic fibers having alkali resistance as described above are used as the envelope material, it is recognized that an increase in pressure loss of the molded adsorbent is suppressed. Nevertheless, the mechanical strength of the molded adsorbent and the effect of improving the moldability that enables it to be molded into a complicated shape are also recognized. This is because the shape of fibrillated polynosic rayon fiber or mercerized natural cellulose fiber has a shape in which many short branches grow from a long trunk, so that it has a high function of strengthening its structure when activated carbon fiber is enveloped. On the other hand, fibrils obtained by beating natural fibers as they are are in a disjointed shape such as thick and short branches irregularly accumulated, and therefore have a function to enhance the structural properties of activated carbon fibers even if they are enveloped. It is thought that this is because there is not enough. As a result of the test by the present inventors, it was recognized that the alkali resistance of the cellulose fiber is apparently the best as a parameter for displaying the envelope function of fibrils as described above.
【0022】本発明において使用されるフィブリル化さ
れた耐アルカリ性セルロース繊維の含有量は、特に限定
しないが成形吸着体の全活性炭繊維の含有量に対して0.
3 %〜20重量%が好ましい。耐アルカリ性セルロース繊
維の含有量が0.3 %以下になると成形吸着体の強度の低
下が著しく実用性がなくなる。また、含有量が20%以上
の場合には成形吸着体の中に占める包絡材の量が多くな
り、吸着性能が低下するので好ましくない。包絡材の含
有量は2%〜10%の範囲内であれば成形吸着体の強度が
高くまた成形体の吸着性能も高いのでより好ましい。The content of the fibrillated alkali-resistant cellulose fibers used in the present invention is not particularly limited, but is 0.
3% to 20% by weight is preferred. When the content of the alkali-resistant cellulose fiber is 0.3% or less, the strength of the molded adsorbent is remarkably reduced and the practicality is lost. Further, if the content is 20% or more, the amount of the envelope material occupying in the shaped adsorbent becomes large and the adsorbability is deteriorated, which is not preferable. If the content of the envelope material is in the range of 2% to 10%, the strength of the shaped adsorbent is high and the adsorbability of the shaped body is also high, which is more preferable.
【0023】耐アルカリ性セルロース繊維のフィブリル
はビーター或いはリファイナーで叩解して得られる。本
発明の活性炭繊維成形吸着体には叩解の度合いが CFS
(カナディアンフリーネス)値で 100〜700 mlが好まし
い。ここで、 CFS値は通常パルプの叩解の度合いを示す
指標として用いられるもので、水を一定量のパルプで濾
過した時の水の透過量で示す。数値が低い程叩解による
パルプの分散と膨潤の度合いが大きいことを示し、数値
が高い程分散及び膨潤性が低いことを示す。The fibrils of alkali-resistant cellulose fibers can be obtained by beating with a beater or refiner. The activated carbon fiber molded adsorbent of the present invention has a beating degree of CFS.
A (Canadian freeness) value of 100 to 700 ml is preferable. Here, the CFS value is generally used as an index showing the degree of beating of pulp, and is indicated by the amount of water permeated when water is filtered through a fixed amount of pulp. A lower value indicates a higher degree of pulp dispersion and swelling due to beating, and a higher value indicates a lower dispersion and swelling property.
【0024】本発明の活性炭繊維成形吸着体には更に湿
潤紙力増強剤を添加しても良い。湿潤紙力増強剤は例え
ば、エポキシ化ポリアミドポリアミンが成形体の湿潤強
度と乾燥強度を共に向上させる効果を有するため好まし
い。A wet paper strength enhancer may be further added to the activated carbon fiber molded adsorbent of the present invention. The wet strength agent is preferable, for example, because epoxidized polyamide polyamine has an effect of improving both the wet strength and the dry strength of the molded body.
【0025】[0025]
【発明の実施の形態】本発明の活性炭繊維成形吸着体は
次の様にして調製することができる。先ず耐アルカリ性
セルロース繊維をビーターあるいはリファイナーによ
り、CFS が100〜700 mlの範囲になるまで叩解する。ア
ルカリ性セルロース繊維は長さ1〜5mm程度に切断した
後、ビーターに投入すると水中の分散状態が良好になる
ため好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The activated carbon fiber molded adsorbent of the present invention can be prepared as follows. First, the alkali-resistant cellulose fiber is beaten with a beater or a refiner until the CFS is in the range of 100 to 700 ml. It is preferable that the alkaline cellulose fiber is cut into a length of about 1 to 5 mm and then put into a beater because the dispersed state in water becomes good.
【0026】次に長さ 0.5〜20mmの範囲に切断した活性
炭のスラリーを調整し、この中に叩解してフィブリル化
したアルカリ性セルロース繊維を2〜10重量%を加え均
一に混合する。混合する際ビーターを使用してもよいし
或いは混合用のスクリューを使用してもよい。スラリー
濃度を0.1 〜5重量%に調製すると吸着体の成形が容易
となるため好ましい。Next, a slurry of activated carbon cut to a length of 0.5 to 20 mm is prepared, and 2 to 10% by weight of beaten and fibrillated alkaline cellulose fibers are added and uniformly mixed. A beater may be used during mixing, or a mixing screw may be used. It is preferable to adjust the slurry concentration to 0.1 to 5% by weight because the adsorbent can be easily molded.
【0027】この活性炭スラリーの中に多数の吸引用小
穴を有する成形用の型枠を入れ、スラリーを吸引・濾過
して吸着体を成形する。スラリーをポンプで吸引するこ
とにより、小穴を有する芯体の表面に活性炭繊維及び包
絡材の混合物を均一に集積することができる。成形され
た成形吸着体は型枠から取り外した後、乾燥して活性炭
繊維成形吸着体が調製される。A mold for molding having a large number of suction holes is put in this activated carbon slurry, and the slurry is sucked and filtered to mold an adsorbent. By sucking the slurry with a pump, the mixture of the activated carbon fiber and the enveloping material can be uniformly accumulated on the surface of the core body having the small holes. The molded adsorbent formed is removed from the mold and then dried to prepare an activated carbon fiber adsorbent.
【0028】本発明の成形吸着体は湿式強度が高いため
型枠から取り外す時に型崩れすることが少なく作成し易
い。乾燥温度は水を蒸発させるため 100℃以上が好まし
いが、80℃以下の低温で乾燥しても強度と耐熱性を有す
る成形吸着体を得ることができるが、乾燥時間が長くな
るため好ましくない。Since the molded adsorbent of the present invention has high wet strength, the molded adsorbent does not easily lose its shape when it is removed from the mold and is easy to manufacture. The drying temperature is preferably 100 ° C. or higher in order to evaporate water, but a molded adsorbent having strength and heat resistance can be obtained even by drying at a low temperature of 80 ° C. or lower, but this is not preferable because the drying time becomes long.
【0029】フィブリル化した耐アルカリ性を有するセ
ルローズ繊維は一定の融点を示さず、高温になるとその
ままの形状で徐々に炭化する性質を持っている。このた
め本発明の活性炭繊維成形吸着体は 120℃以上の耐熱性
を有し、150 ℃以上の温度でも使用可能である。活性炭
繊維は吸着性能が優れ、再生も粒状活性炭と比較し低温
・短時間で行うことができる。しかし、活性炭繊維の再
生には少なくとも 100℃以上の温度は必要であり、好ま
しくは 120℃以上である。本発明の成形吸着体は 120℃
以上での強度低下が非常に少ないため、活性炭繊維成形
吸着体として高温の雰囲気で広く使用可能である。The fibrillated cellulose fibers having alkali resistance do not show a certain melting point and have the property of gradually carbonizing in the same shape at high temperature. Therefore, the activated carbon fiber molded adsorbent of the present invention has a heat resistance of 120 ° C or higher and can be used even at a temperature of 150 ° C or higher. Activated carbon fiber has excellent adsorption performance and can be regenerated at low temperature and in a shorter time than granular activated carbon. However, regeneration of the activated carbon fiber requires a temperature of at least 100 ° C or higher, preferably 120 ° C or higher. The molded adsorbent of the present invention has a temperature of 120 ° C.
Since the strength decrease by the above is extremely small, it can be widely used in a high temperature atmosphere as an activated carbon fiber molded adsorbent.
【0030】このため本発明の活性炭繊維成形吸着体は
従来の成形吸着体に較べて、より高温における再生処理
が可能となり、従って、吸着性回復率が高く再生から次
の再生迄の使用期間も伸び、更に成形吸着体全体の寿命
も長くなる。Therefore, the activated carbon fiber shaped adsorbent of the present invention can be regenerated at a higher temperature than conventional shaped adsorbents, and therefore has a high adsorbent recovery rate and can be used from one regeneration to the next regeneration. In addition, the life of the entire shaped adsorbent is extended.
【0031】本発明の活性炭繊維成形吸着体は液相及び
気相における微量不純物及び有害成分の吸着除去用に使
用することができる。例えば、浄水器フィルター(残留
塩素の除去、トリハロメタン等の有機塩素化合物の除
去、カビ臭の除去)または空気清浄器用フィルター、メ
ッキ等の廃液の処理、有機塩素化合物の溶剤回収等に使
用することができる。The activated carbon fiber shaped adsorbent of the present invention can be used for adsorption and removal of trace impurities and harmful components in a liquid phase and a gas phase. For example, it can be used for water purifier filters (removal of residual chlorine, removal of organic chlorine compounds such as trihalomethane, removal of mold odor) or filters for air purifiers, treatment of waste liquid such as plating, solvent recovery of organic chlorine compounds, etc. it can.
【0032】[0032]
【実施例】以下、実施例を挙げて本発明を更に具体的に
説明する。EXAMPLES The present invention will be described in more detail below with reference to examples.
【0033】(実施例1)図1に本発明の活性炭繊維成
形吸着体調製用の型枠の斜視図を、図2に本実施例で得
られた本発明の活性炭繊維成形吸着体の一態様の斜視図
を示す。Example 1 FIG. 1 is a perspective view of a mold for preparing the activated carbon fiber molded adsorbent of the present invention, and FIG. 2 is a mode of the activated carbon fiber molded adsorbent of the present invention obtained in this example. FIG.
【0034】ポリノジックレーヨン繊維 (2d×3mm)を、
ビーターでCSF が 400mlまで叩解した。平均繊維長が20
mm程度になるまで切断した活性炭素繊維を1kg(比表面積
1500m2/g) とビーターで叩解したポリノジックレーヨン
繊維50g(活性炭素繊維に対して5%混合)をビーターに
入れ、混合と叩解を行って活性炭繊維が叩解により生成
したポリノジックレーヨン繊維のフィブリルで充分に包
絡された状態にした。この調製済スラリーをタンクに入
れ吸引成形用のスラリーとした。Polynosic rayon fiber (2d × 3 mm)
The beater beaten the CSF to 400 ml. Average fiber length is 20
1 kg of activated carbon fiber cut to about mm (specific surface area
1500m 2 / g) and 50g of polynosic rayon fiber beaten with a beater (5% mixed with activated carbon fiber) are put into a beater, mixed and beaten, and the fibrils of polynosic rayon fiber produced by beating are sufficient. It was enveloped in. This prepared slurry was put into a tank to prepare a slurry for suction molding.
【0035】吸着体成形用型枠の芯体1の表面に多数の
吸引用小孔を設け、両端に盲フランジ2、3(直径65m
m) ジを取り付けた円筒状の成形用型枠 (外径30mm、長
さ250mm) を混合スラリーの中に入れ、吸引ポンプで芯
体の内部からスラリーを吸引し、成形型枠の芯体の周囲
に活性炭繊維とフィブリル化したポリノジックレーヨン
繊維の混合物を付着させた。この様にして中空円筒型の
吸着体を生成させた。A large number of suction holes are provided on the surface of the core 1 of the adsorbent molding frame, and blind flanges 2 and 3 (diameter 65 m are provided at both ends.
m) Put a cylindrical molding frame (outer diameter 30 mm, length 250 mm) equipped with a jig into the mixed slurry and suck the slurry from the inside of the core with a suction pump to remove the core of the molding frame. A mixture of activated carbon fibers and fibrillated polynosic rayon fibers was deposited around the periphery. In this way, a hollow cylindrical adsorbent was produced.
【0036】両端の盲フランジを取り除き、成形体から
芯体を抜き取った。本成形体は湿式強度 (湿潤状態での
強度) が高いために芯体は容易に引き抜くことができ
た。湿潤状態の成形体から芯体を抜く時、湿式強度が弱
い成形体では形が崩れる場合が多く、成形体の収率が低
いことが大きな問題であったが、本成形体ではこの問題
は大幅に改良されていた。The blind flanges on both ends were removed, and the core was removed from the molded body. Since the formed body has high wet strength (strength in a wet state), the core body could be easily pulled out. When removing a core from a wet molded body, the shape of the molded body with weak wet strength often collapses, and the problem was that the yield of the molded body was low. Had been improved to.
【0037】この成形体を 120℃で12時間加熱乾燥を行
い成形吸着体を得た。得られた成形吸着体は内径30mm、
外径65mm、長さ250 mmで、この成形体の密度は0.18 g/c
c であった。この成形体の比表面積は 1300m2/g (N2 ガ
スを使用してB.E.T.法で測定) で充分実用性を有するこ
とが認められた。The molded body was heated and dried at 120 ° C. for 12 hours to obtain a molded adsorbent. The obtained molded adsorbent has an inner diameter of 30 mm,
With an outer diameter of 65 mm and a length of 250 mm, the density of this molding is 0.18 g / c
It was c. It was confirmed that the specific surface area of this molded body was 1300 m 2 / g (measured by the BET method using N 2 gas), which was sufficiently practical.
【0038】この成形体の25℃および 140℃における強
度を表1に示した。成形体を4mm圧縮するのに必要な最
大加重を成形吸着体の強度とした。強度および耐熱性は
良好であった。また、成形体に10リットル/minの流量で
水を流した場合の圧力損失が低く充分に実用性が認めら
れた。The strength of this molded product at 25 ° C. and 140 ° C. is shown in Table 1. The maximum load required to compress the compact by 4 mm was defined as the strength of the compact adsorbent. The strength and heat resistance were good. Further, the pressure loss when water was flown through the molded body at a flow rate of 10 liters / min was low, and the practicability was sufficiently confirmed.
【0039】[0039]
【表1】 [Table 1]
【0040】前記で得られた成形吸着体にトリハロメタ
ン60 ppb (クロロホルム30 ppb、クロロジブロモメタン
10 ppb、ジクロロブロモメタン10 ppb、ブロモメタン10
ppb) を含む水を流量 10 リットル/min. で通水した。
4000リットル通水時のトリハロメタンの除去率は 80 %
であった。60 ppb of trihalomethane (30 ppb of chloroform, chlorodibromomethane) was added to the shaped adsorbent obtained above.
10 ppb, dichlorobromomethane 10 ppb, bromomethane 10
Water containing ppb) was passed at a flow rate of 10 liters / min.
Removal rate of trihalomethane is 80% when passing 4000 liters of water.
Met.
【0041】この成形体に 150℃のスチームを20分間通
して再生した後トリハロメタン 60ppb を含む水を通水
した。通水初期のトリハロメタン除去率は 100%、4000
リットル通水時点での除去率は 80 %であり、トリハロ
メタンの吸着性能は完全に再生されていた。The molded body was regenerated by passing steam at 150 ° C. for 20 minutes, and then water containing 60 ppb of trihalomethane was passed through. Trihalomethane removal rate at the beginning of water flow is 100%, 4000
The removal rate at the time of passing liter of water was 80%, and the adsorption performance of trihalomethane was completely regenerated.
【0042】更に、ポリノジックレーヨン繊維を40℃の
水酸化カリウム溶液 (20重量%) に20日間浸漬して強度
の変化を観察した。この繊維は20日後も高い強度を有し
ており、アルカリ溶液に浸すことによっても強度の低下
がなく耐アルカリ性が高いことが認められた。また繊維
からの溶出物によりアルカリ溶液が汚れることももなか
った。Further, the polynosic rayon fiber was immersed in a potassium hydroxide solution (20% by weight) at 40 ° C. for 20 days, and the change in strength was observed. It was confirmed that this fiber had a high strength even after 20 days, and that the strength did not decrease even when immersed in an alkaline solution, and the alkali resistance was high. Moreover, the alkaline solution was not contaminated by the eluate from the fiber.
【0043】(実施例2)マーセル化された広葉樹木材
パルプを、ダブルディスクリファイナーでCSF が400 ml
まで叩解した。これを 50g (活性炭繊維に対して5%使
用した以外は実施例1と同様にして活性炭繊維成形吸着
体を作った。この耐熱性と圧力損失を測定し表1に示し
た。この成形体は湿式強度が高く作成も容易であった。
乾燥後の成形体は強度が高くまた耐熱性も良好であり、
更に圧力損失も低く充分実用に耐える性能を有してい
た。(Example 2) Mercerized hardwood wood pulp was mixed with a double disc refiner to obtain CSF of 400 ml.
I beat up. An activated carbon fiber molded adsorbent was prepared in the same manner as in Example 1 except that 50 g (5% based on activated carbon fiber) was used. The heat resistance and pressure loss were measured and shown in Table 1. It had high wet strength and was easy to prepare.
The molded product after drying has high strength and good heat resistance,
Furthermore, the pressure loss was low and the performance was sufficient for practical use.
【0044】マーセル化した広葉樹木材パルプの耐アル
カリ性を実施例1と同様にして測定した。強度の低下は
認められず耐アルカリ性は良好であった。また繊維から
の溶出物によりアルカリ溶液が汚れることもなかった。The alkali resistance of the mercerized hardwood wood pulp was measured in the same manner as in Example 1. No reduction in strength was observed and the alkali resistance was good. Further, the alkaline solution was not contaminated by the eluate from the fiber.
【0045】(実施例3)実施例1と同様にして叩解し
たポリノジックレーヨン繊維50g(活性炭素繊維に対して
5%) と、湿潤紙力増強剤エポキシ化ポリアミドアミン
を10g(活性炭素繊維に対して1%) 添加した以外は、実
施例1と同様にして成形体を調製した。成形体の湿式強
度は良好であり作成も容易であった。乾燥した成形体の
強度及び耐熱性も良好であり、また圧力損失も低く実用
性が高い吸着体が得られた。成形体の物性を表1に示し
た。Example 3 50 g of polynosic rayon fiber beaten in the same manner as in Example 1 (5% based on activated carbon fiber) and 10 g of wet paper strength enhancer epoxidized polyamidoamine (based on activated carbon fiber) A molded body was prepared in the same manner as in Example 1 except that the addition amount was 1%). The wet strength of the molded body was good and the molding was easy. An adsorbent having good strength and heat resistance, a low pressure loss, and high practicality was obtained. The physical properties of the molded product are shown in Table 1.
【0046】(比較例1)広葉樹木材パルプをダブルデ
ィスクリファイナーでCSF が400ml まで叩解した。これ
を使用した以外は実施例1と同様にして活性炭繊維成形
吸着体を作った。この成形体の物性を表1に示した。こ
の成形体の湿式強度は高く作成が容易であった。乾燥後
の成形体の強度は耐アルカリ性を有するセルロース繊維
を使用した場合と比較して低く実用性はなかった。また
この成形体の圧力損失は高く実用性が乏しかった。Comparative Example 1 Hardwood wood pulp was beaten with a double disc refiner to a CSF of 400 ml. An activated carbon fiber molded adsorbent was produced in the same manner as in Example 1 except that this was used. The physical properties of this molded product are shown in Table 1. The wet strength of this molded body was high and it was easy to prepare. The strength of the molded product after drying was low as compared with the case where the cellulose fiber having alkali resistance was used and was not practical. Further, the pressure loss of this molded body was high and the practicality was poor.
【0047】広葉樹木材パルプの耐アルカリ性を実施例
1と同様にして測定した。アルカリ溶液が汚れたことに
よりパルプからの溶出があることが分かった。パルプの
強度は低下しており、このパルプは耐アルカリ性が乏し
かった。The alkali resistance of hardwood wood pulp was measured in the same manner as in Example 1. It was found that there was elution from the pulp due to the soiling of the alkaline solution. The strength of the pulp was reduced and the pulp had poor alkali resistance.
【0048】(比較例2)広葉樹木材パルプをダブルデ
ィスクリファイナーでCSF が400ml まで叩解した。これ
を25g(活性炭繊維に対して2.5 %) と軟化点80℃のポリ
アクリロニトリル繊維25g(活性炭繊維に対して2.5 %)
を使用した以外は実施例1と同様にして成形体を作成し
た。この成形体の湿式強度は弱く、芯体を抜く場合に湿
潤状態の成形体が型くずれすることが多かった。この成
形体を実施例1と同じ条件で乾燥した。得られた成形体
の25℃の強度及び 140℃での強度を表1に示す。 140℃
では強度が大幅に低下し、この成形体は耐熱性に乏しい
ことが分かった。Comparative Example 2 Hardwood wood pulp was beaten to a CSF of 400 ml with a double disc refiner. 25 g of this (2.5% based on activated carbon fiber) and 25 g of polyacrylonitrile fiber with a softening point of 80 ° C (2.5% based on activated carbon fiber)
A molded body was prepared in the same manner as in Example 1 except that was used. The wet strength of this molded product was weak, and the molded product in a wet state often lost its shape when the core was removed. This molded body was dried under the same conditions as in Example 1. Table 1 shows the strength at 25 ° C and the strength at 140 ° C of the obtained molded body. 140 ° C
Then, the strength was significantly reduced, and it was found that this molded body had poor heat resistance.
【0049】(比較例3)軟化点80℃のポリアクリロニ
トリル繊維50g を叩解せずに使用した以外は実施例1と
同様にして成形体を作成した。この成形体の湿式強度は
極めて弱く、芯体を抜く場合には殆どの成形体が崩れ
た。ごく一部崩れない成形体が得られたためこの成形体
を 100℃で18時間乾燥した。 140℃で乾燥した場合には
成形体が崩れた。乾燥後の成形体の強度を測定したが 1
40℃での強度は極めて弱く実用性はなかった。この成形
体の物性を表1に示した。Comparative Example 3 A molded product was prepared in the same manner as in Example 1 except that 50 g of polyacrylonitrile fiber having a softening point of 80 ° C. was used without beating. The wet strength of this molded product was extremely weak, and most of the molded product collapsed when the core was removed. Since a molded product which was not partially broken was obtained, this molded product was dried at 100 ° C. for 18 hours. The molded body collapsed when dried at 140 ° C. The strength of the molded body after drying was measured.
The strength at 40 ° C was extremely weak and not practical. The physical properties of this molded product are shown in Table 1.
【0050】前記で得られた吸着成形体を実施例1のト
リハロメタンの吸着試験と同一の条件でトリハロメタン
を含む水を通してその除去率を測定した。4000リットル
通水時点での除去率は実施例1の場合と同様に80%であ
った。The removal rate of the adsorption molded body obtained above was passed through water containing trihalomethane under the same conditions as in the adsorption test of trihalomethane of Example 1. The removal rate at the time of passing 4000 liters was 80% as in the case of Example 1.
【0051】この成形体に75℃の温水を20分通して再生
した後、トリハロメタンを含む水を通したところ通水開
始直後のトリハロメタン除去率は 90 %であり、700 リ
ットル通水時点での除去率は 80 %に低下した。この成
形体は 80 ℃以上に加熱すると強度が急激に低下する現
象が認められるため、充分な再生処理をすることか困難
であった。After the hot water of 75 ° C. was regenerated through this molded body for 20 minutes and then water containing trihalomethane was passed through, the removal rate of trihalomethane was 90% immediately after the start of water flow. The rate dropped to 80%. It was difficult to sufficiently regenerate the molded product because it was observed that the strength of the molded product dropped sharply when heated to 80 ° C or higher.
【0052】(実施例4)実施例1においてポリノジッ
クレーヨン繊維を 150g とした以外は同じ条件で成形体
を作成しその物性を測定した。その結果を表1に示す。
活性炭繊維の比率が下がっているため比表面積測定値は
少し低下しているが強度、圧力損失共に良好で、充分に
使用可能であった。Example 4 A molded product was prepared under the same conditions as in Example 1 except that the polynosic rayon fiber was changed to 150 g, and its physical properties were measured. The results are shown in Table 1.
The measured value of the specific surface area was slightly lowered because the ratio of the activated carbon fiber was lowered, but the strength and the pressure loss were good, and it was possible to sufficiently use it.
【0053】(比較例4)実施例1においてポリノジッ
クレーヨン繊維を 250g とした以外は同じ条件で成形体
を作成しその物性を測定した。その結果を表1に示す。
強度は優れているが圧力損失はかなり上昇している。成
形体の比表面積が大幅に低下しており実用性は不十分で
あった。比表面積が低下した理由は包絡材の比率が増加
したため活性炭繊維の表面の一部が被覆されたためと考
えられる。Comparative Example 4 A molded product was prepared under the same conditions as in Example 1 except that the polynosic rayon fiber was 250 g, and the physical properties were measured. The results are shown in Table 1.
The strength is excellent, but the pressure loss is considerably increased. The specific surface area of the molded product was significantly reduced, and its practicality was insufficient. It is considered that the reason why the specific surface area decreased is that the ratio of the enveloping material increased and thus a part of the surface of the activated carbon fiber was covered.
【0054】[0054]
【発明の効果】本発明は主成分として活性炭繊維及び包
絡材としてフィブリル化した耐アルカリ性セルローズ繊
維を含む活性炭繊維成形吸着体で、湿潤強度、高温での
強度も高く耐熱性が優れているため再生処理による吸着
性回復率が高い特徴がある。液相及び気相における微量
不純物及び有害成分の吸着除去用に使用することができ
る。例えば、浄水器フィルターまたは空気清浄器用フィ
ルター、溶剤回収等に適している。Industrial Applicability The present invention is an activated carbon fiber molded adsorbent containing activated carbon fibers as main components and fibrillated alkali-resistant cellulose fibers as an enveloping material, which has high wet strength, high strength at high temperature, and excellent heat resistance. It is characterized by a high recovery rate of adsorptivity due to treatment. It can be used for adsorptive removal of trace impurities and harmful components in liquid and gas phases. For example, it is suitable for a water purifier filter or an air purifier filter, solvent recovery, and the like.
【図1】本発明の活性炭繊維成形吸着体調製用の型枠の
斜視図を示す。FIG. 1 shows a perspective view of a mold for preparing an activated carbon fiber molded adsorbent of the present invention.
【図2】実施例1で得られた本発明の活性炭繊維成形吸
着体の一態様の斜視図を示す。2 shows a perspective view of one embodiment of the activated carbon fiber molded adsorbent of the present invention obtained in Example 1. FIG.
1 成形吸着体調製用の型枠 2 型枠の芯体 3 芯体の吸引用小孔 4、4′型枠のフランジ 5 濾液出口 6 活性炭繊維成形吸着体 1 Formwork for molding adsorbent preparation 2 Formwork core 3 Small core suction holes 4,4 'formwork flange 5 Filtrate outlet 6 Activated carbon fiber molded adsorbent
Claims (3)
てフィブリル化した耐アルカリ性セルローズ繊維を含む
活性炭繊維成形吸着体であって、フィブリル化した耐ア
ルカリ性セルローズ繊維の含有量が活性炭繊維100重
量部に対して、0.3〜20重量部である活性炭繊維成
形吸着体。 1. A activated carbon fiber molded adsorbent comprising alkali-resistant cellulose fibers fibrillated as activated carbon fibers and the envelope material as the main component,耐A fibrillated
The content of Lucari cellulose fiber is 100 weight of activated carbon fiber.
0.3 to 20 parts by weight based on the amount of activated carbon fiber composition
Shaped adsorbent.
繊維である請求項1記載の活性炭繊維成形吸着体。2. The activated carbon fiber molded adsorbent according to claim 1, wherein the cellulosic fibers are polynosic rayon fibers.
ーズ繊維である請求項1記載の活性炭繊維成形吸着体。3. The activated carbon fiber molded adsorbent according to claim 1, wherein the cellulose fibers are mercerized natural cellulose fibers.
Priority Applications (1)
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JP18418696A JP3516811B2 (en) | 1996-06-24 | 1996-06-24 | Activated carbon fiber molded adsorbent |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP18418696A JP3516811B2 (en) | 1996-06-24 | 1996-06-24 | Activated carbon fiber molded adsorbent |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH105580A JPH105580A (en) | 1998-01-13 |
JP3516811B2 true JP3516811B2 (en) | 2004-04-05 |
Family
ID=16148871
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JP18418696A Expired - Fee Related JP3516811B2 (en) | 1996-06-24 | 1996-06-24 | Activated carbon fiber molded adsorbent |
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WO2013191269A1 (en) | 2012-06-22 | 2013-12-27 | クラレケミカル株式会社 | Activated carbon for noble metal adsorption, noble metal adsorption filter, and method for recovering noble metals |
US9033158B2 (en) | 2009-08-06 | 2015-05-19 | Kuraray Chemical Co., Ltd. | Molded activated charcoal and water purifier involving same |
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1996
- 1996-06-24 JP JP18418696A patent/JP3516811B2/en not_active Expired - Fee Related
Cited By (2)
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---|---|---|---|---|
US9033158B2 (en) | 2009-08-06 | 2015-05-19 | Kuraray Chemical Co., Ltd. | Molded activated charcoal and water purifier involving same |
WO2013191269A1 (en) | 2012-06-22 | 2013-12-27 | クラレケミカル株式会社 | Activated carbon for noble metal adsorption, noble metal adsorption filter, and method for recovering noble metals |
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JPH105580A (en) | 1998-01-13 |
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