JPH0534045B2

JPH0534045B2 -

Info

Publication number: JPH0534045B2
Application number: JP63196099A
Authority: JP
Inventors: Hisashi Kojima; Masaji Kurosawa; Isao Terada; Hideto Nakada
Original assignee: Nichias Corp; Tokyo Roki Co Ltd
Current assignee: Nichias Corp; Tokyo Roki Co Ltd
Priority date: 1988-08-08
Filing date: 1988-08-08
Publication date: 1993-05-21
Also published as: JPH0248015A

Description

[Detailed description of the invention]

≪産業上の利用分野≫ 本発明は、活性炭を担持し、ガス吸着能やオゾ
ン分解能を有するハニカム構造体およびその製造
方法に関するものである。 ≪従来の技術と技術的課題≫ 特定の成分の吸着または分解のための気体活性
炭処理において、被処理気体の流量が大である場
合、活性炭は極力圧力損失が低くなるような状態
で処理に供することが望ましい。このような観点
から、特開昭60−90808号公報の発明では、活性
炭素材をハニカム状に押出成形した後、炭素化し
賦活したものを、オゾン分解用活性炭ハニカム構
造体として提案している。このハニカム構造体は、単位体積当たりの活性
炭量が300ｇ／であり、ベンゼン、メタノール
など吸着量が50mg／、80時間経過後のオゾン分
解効率は85％と、性能が高い。しかしながら、押出成形によつて大型かつ強固
なハニカム構造体を製造することは困難であるか
ら、この型のハニカム構造体としては小形のもの
しか使えないという問題があつた。また、このようにほとんど活性炭からなるハニ
カム構造体は、吸着能は大きくても、押出し中に
活性炭が固まるため、活性炭全体を吸着面として
有効に用いているとは言えないほか、成形後に賦
活処理するなどの面倒な処理を必要とし、高価で
割れやすいため取扱が面倒であるという問題もあ
つた。これに対して、パルプ等からなる有機繊維と活
性炭との混合物から紙を抄造し、得られた活性炭
含有紙から活性炭担持ハニカム構造体を製造する
方法も知られている。しかし、この方法では紙の抄造工程で活性炭を
抄きこむため、活性炭含有率を高くできず、最大
限で単位体積当たりの活性炭量が65ｇ／、ベン
ゼンなどの吸着量が23mg／、80時間経過後のオ
ゾン分解効率が48％程度にしか出来ないため、こ
のハニカム構造体の初期オゾン分解能は一応実用
程度には得られるが、寿命の点で満足できるもの
ではなく、前記押出成形体からなるハニカム構造
体に比べて寿命性能上の落差がおおきかつた。そこで本発明は、必要に応じていかなる大きな
ハニカム構造体でも容易に製作でき、従来の活性
炭担持ハニカム構造体に比較して活性炭の含有量
が飛躍的に大きく、またその吸着能を最大限利用
することが可能な活性炭担持ハニカム構造体、お
よびその製造方法を提供することを目的とするも
のである。 ≪課題を解決するための手段≫ 前記目的を達成するため、本発明は、繊維空〓
率85〜95％の高空〓率無機繊維製紙および該紙の
繊維間間〓に120〜150ｇ／の割合で充填固定さ
れた吸着量40mg／以上の活性炭よりなるハニカ
ム構造体を提供するものである。さらに本発明では、以下にのべるハニカム構造
体の製造方法を提供するものである。すなわち、本発明の製造方法は、微粉末状活性
炭およびこの活性炭重量の1/9〜1/10の量のアク
リル系バインダー、塩化ビニリデン系バインダ
ー、コロイダルシリカから選ばれた結合剤の懸濁
液に、繊維空〓率85〜95％の無機繊維製紙を浸漬
するか、または前記懸濁液を無機繊維製紙に塗布
したのちに乾燥することにより、前記紙の繊維間
間〓に120〜150ｇ／の割合で活性炭を充填し、
該活性炭が充填された紙およびそれをコルゲート
加工したものを交互に重ねて接着し、通気方向に
対して所定の開口率のハニカム構造体を形成する
ことを特徴とする。次に、本発明のさらに好ましい製造方法につい
て詳述する。紙を抄造する無機繊維としては、Ｅガラスまた
はＣガラスからなる太さ６〜9μｍ程度、長さ８
〜12mm程度のガラス繊維が用いられる。ただし、これらガラス繊維に限定されるわけで
はない。無機繊維の抄造は、常法により行い、その結果
繊維間空〓率が85〜95％、かつ厚さが0.10〜0.30
mm、好ましくは0.15〜0.25mmの紙に形成される。得られた紙に活性炭を充填するが、その際用い
る活性炭は、平均粒径５〜40μｍ、吸着量1170
mg／ｇの微粉末が用いられる。充填方法は以下の工程で行なわれる。まず、前記活性炭を活性炭重量に対して1/9〜
１／１０量の結合剤とともに水に懸濁させる。結合剤としては、例えばアクリル系、塩化ビニ
リデン系、コロイダルシリカなどの乾燥後も柔軟
性を維持するものが、以下にのべるコルゲート加
工を容易にする。そして、この懸濁液を浸漬または塗布により、
紙に吸収させる。なお、以上の活性炭懸濁液に有機含リン含窒素
化合物、三酸化アンチモン等の難燃剤を加えてお
くと、難燃性の製品が得られる。これの適量は活
性炭重量の1/50〜1/15量であり、これを下回ると
難燃効果がなく、また上回つた場合にはその分活
性炭含有量が低くなり分解能に影響を与えるの
で、上記の範囲内の添加量が好ましい。次いで乾燥によつて、活性炭は繊維間〓に充填
された状態で結合剤を介して繊維間〓に固定され
る。紙の空〓率が85％以上あれば、この方法により
120〜150ｇ／の活性炭を紙に充填することがで
き、これだけの量の活性炭を充填すると繊維の重
量に対して100〜400％の量の活性炭が付着させら
れる。得られた活性炭充填紙の一部を常法によりコル
ゲート加工する。そして、第１図に示すように、コルゲート加工
した紙１と無加工の平らな紙２とを交互に重ね合
わせ、それらの接点において接着することによ
り、第２図に示すハニカム構造体を得られる。両者の接着に用いる接着剤としては、前記と同
様アクリル系バインダー、コロイダルシリカを使
用できる。以上の製造方法によつて得られた製品は、あら
ためて賦活処理を施することなしに気体処理に供
することができる。 ≪作用、効果≫ 本発明の活性炭担持ハニカム構造体は、上述の
ように高空〓率の無機質繊維製紙の繊維間間〓に
多量の活性炭を充填したものであるから、押出成
形法による活性炭ハニカム構造体に比べて、とう
てい製造不可能な大型のものも容易に製造するこ
とができる。また、活性炭量と吸着量の比率が押
出成形体が300：50であるのに対し、本発明が
136：40であり、活性炭量の割りには吸着能が高
い。また、かさばるハニカム構造体に成形してから
の賦活処理が不要であるから、安価に製造できる
ばかりでなく、寸法精度のよい製品を容易に得る
ことができる。さらに無機繊維が骨格となつてい
るため、湿度による寸法変化が小さく、耐薬品性
や耐久性も良好である。本発明を、従来の活性炭を漉きこんだ紙をハニ
カム構造体にしたものと比べた場合には、従来の
活性炭担持量の最大値が紙体積の約65ｇ／であ
るのに比べ、本発明では120〜150ｇ／とはるか
に多くすることができ、またベンゼン、アルコー
ルなどの吸着量が従来のものが23mg／であるの
に対し、本発明が、40mg／以上と、約２倍の値
を示し、また、80時間経過後のオゾン分解効率が
従来が48％であるのに対し、72％となり、分解性
能にすぐれる。また、活性炭を漉きこむ場合、従来では抄造工
程における高価な活性炭の損失が避けられない
が、紙の抄造後に活性炭を充填する本発明の製造
方法では、活性炭の損失がほとんど無い。担持される活性炭が抄造性や、押出成形性など
によつて制限されず、その種類、特性の選択に自
由度が高いことも本発明の有利な点である。さらに、活性炭とともに難燃剤を担持させたも
のは、無機繊維が骨格となつていることもあつ
て、高度の難燃性を示す。上述する特徴を生かして、本発明のハニカム構
造体は例えば電子複写機その他の機器のオゾン分
解用フイルター、各種脱臭剤用フイルター、触媒
担持体などに有効に利用できる。 ≪実施例≫ 以下、本発明の実施例を説明する。ただし、本
発明は以下の実施例のみに限定されるものではな
い。実施例１Ｅガラス繊維（繊維径9μｍ、繊維長８mm）を
用いて常法により厚さ0.2mm、繊維間空〓率94％
の紙を抄造し、この紙に粒度５〜40μｍ、比表面
積1300m²／ｇ（吸着量1170mg／ｇ）の活性炭と、
活性炭重量の1/10量のアクリル系バインダーとを
含む懸濁液を塗布した後、乾燥した。得られた活性炭充填紙（活性炭充填量136ｇ／
紙体積、重量90ｇ／m²）の一部をコルゲール加
工した。そして、第１図に示すように、コルゲー
ト加工した紙１と無加工の平らな紙２との交互に
重ね合わせ、それらの接点において増粘剤を加え
たアクリル系バインダーで接着することにより、
第２図に示すハニカム構造体を得た。このハニカム構造体のピツチ（セル幅）は3.2
mm、セル高さは1.2mm、開口率は63％であつた。以上の方法によつて得た活性炭担持ハニカム構
造体について、下記の条件でオゾン分解性能を調
べた。通気風速：1.0ｍ／Sec 通気オゾン濃度：1.2ppm 通気方向のハニカム構造体厚さ：20mm その結果を第３図に示す。比較例比較のため、ほぼ限界量の活性炭を漉きこんだ
有機繊維からなる紙から製造した前記と同一寸法
の活性炭担持ハニカム構造体（活性炭量65ｇ／
）についても同様の試験を行つた。この結果も第３図に示す。実施例２実施例１と同様のハニカム構造体製造例におい
て、塗布用活性炭含有スラリー中に活性炭重量の
10％の有機含リン含窒素化合物からなる難燃剤を
添加した。得られた活性炭担持ハニカム構造体
は、当然ながら高度の難燃性を示した。またこのハニカム構造体についても実施例１と
同様の試験を行つた。その結果も第３図中に示されている。そして、図からも明らかなように実施例１、２
で示す本発明のハニカム構造体のオゾン分解率
は、比較例に比して初期状態ではほとんど同じで
あるが、処理時間の経過に対するベンゼンなどの
有機溶媒の吸着能の低下勾配が小さく、持続的な
効果があることが判明している。また、従来の押出成形体のものと有機繊維を抄
造したハニカム構造体、および本発明のハニカム
構造体の特性を比較したものを以下の表に一括し
て示す。 <<Industrial Application Field>> The present invention relates to a honeycomb structure supporting activated carbon and having gas adsorption ability and ozone decomposition ability, and a method for manufacturing the same. <<Prior art and technical issues>> In gaseous activated carbon treatment for adsorption or decomposition of specific components, when the flow rate of the gas to be treated is large, the activated carbon is subjected to the treatment in a state that reduces pressure loss as much as possible. This is desirable. From this point of view, the invention of JP-A-60-90808 proposes an activated carbon honeycomb structure for ozonolysis in which an activated carbon material is extruded into a honeycomb shape and then carbonized and activated. This honeycomb structure has high performance, with an amount of activated carbon per unit volume of 300 g, an adsorption amount of benzene, methanol, etc. of 50 mg/, and an ozone decomposition efficiency of 85% after 80 hours. However, since it is difficult to manufacture large and strong honeycomb structures by extrusion molding, there is a problem that only small honeycomb structures of this type can be used. In addition, although the honeycomb structure made mostly of activated carbon has a high adsorption capacity, the activated carbon solidifies during extrusion, so it cannot be said that the entire activated carbon is effectively used as an adsorption surface. There were also problems in that it required troublesome processing such as washing, was expensive, and was easy to break, making it troublesome to handle. On the other hand, a method is also known in which paper is made from a mixture of organic fibers such as pulp and activated carbon, and an activated carbon-supporting honeycomb structure is manufactured from the obtained activated carbon-containing paper. However, with this method, activated carbon is incorporated during the paper making process, so it is not possible to increase the activated carbon content, and the maximum amount of activated carbon per unit volume is 65g/unit volume, and the adsorption amount of benzene, etc. is 23mg/, after 80 hours. Since the ozone decomposition efficiency of this honeycomb structure is only about 48%, the initial ozone decomposition efficiency of this honeycomb structure can be obtained at a practical level, but it is not satisfactory in terms of life. There was a large difference in lifespan performance compared to the body. Therefore, the present invention can easily produce any large honeycomb structure as required, has a dramatically higher activated carbon content than conventional activated carbon-supported honeycomb structures, and makes maximum use of its adsorption capacity. The object of the present invention is to provide an activated carbon-supported honeycomb structure that can be used in the present invention, and a method for manufacturing the same. ≪Means for Solving the Problems≫ In order to achieve the above object, the present invention provides fiber hollow
The present invention provides a high porosity inorganic fiber paper with a void ratio of 85 to 95%, and a honeycomb structure made of activated carbon with an adsorption amount of 40 mg/or more, which is filled and fixed between the fibers of the paper at a ratio of 120 to 150 g/. . Furthermore, the present invention provides the following method for manufacturing a honeycomb structure. That is, the production method of the present invention involves adding a suspension of finely powdered activated carbon and a binder selected from acrylic binder, vinylidene chloride binder, and colloidal silica in an amount of 1/9 to 1/10 of the weight of the activated carbon. , by dipping inorganic fiber paper with a fiber vacancy rate of 85 to 95%, or by applying the suspension to inorganic fiber paper and drying it, 120 to 150 g/g/g of paper is added between the fibers of the paper. Filled with activated carbon in proportion,
The method is characterized in that the activated carbon-filled paper and its corrugated paper are alternately stacked and bonded to form a honeycomb structure having a predetermined open area ratio in the ventilation direction. Next, a more preferred manufacturing method of the present invention will be described in detail. Inorganic fibers for making paper include E glass or C glass, about 6 to 9 μm in thickness and 8 in length.
Glass fiber of about 12 mm is used. However, it is not limited to these glass fibers. The inorganic fibers are produced using a conventional method, resulting in an interfiber porosity of 85 to 95% and a thickness of 0.10 to 0.30.
mm, preferably 0.15-0.25 mm paper. The obtained paper is filled with activated carbon, and the activated carbon used at that time has an average particle size of 5 to 40 μm and an adsorption amount of 1170 μm.
A fine powder of mg/g is used. The filling method is performed in the following steps. First, add the activated carbon to 1/9 to 1/9 of the activated carbon weight.
Suspend in water with 1/10 amount of binder. As a binder, a binder that maintains flexibility even after drying, such as acrylic, vinylidene chloride, or colloidal silica, facilitates the corrugating process described below. Then, by dipping or applying this suspension,
Absorb into paper. Incidentally, a flame retardant product can be obtained by adding a flame retardant such as an organic phosphorus-containing nitrogen-containing compound or antimony trioxide to the above activated carbon suspension. The appropriate amount of this is 1/50 to 1/15 of the weight of activated carbon; if it is less than this, there will be no flame retardant effect, and if it is more than this, the activated carbon content will be reduced by that amount and will affect the resolution. The amount added is preferably within the above range. Next, by drying, the activated carbon is fixed between the fibers via a binder while being filled between the fibers. If the paper empty rate is 85% or more, use this method.
The paper can be loaded with 120 to 150 g of activated carbon, and when this amount of activated carbon is loaded, the activated carbon is deposited in an amount of 100 to 400% based on the weight of the fibers. A part of the obtained activated carbon-filled paper is corrugated by a conventional method. Then, as shown in Fig. 1, corrugated paper 1 and unprocessed flat paper 2 are alternately stacked and bonded at their contact points, thereby obtaining the honeycomb structure shown in Fig. 2. . As the adhesive used to bond the two, an acrylic binder and colloidal silica can be used as described above. The product obtained by the above manufacturing method can be subjected to gas treatment without additional activation treatment. <<Operations and Effects>> The activated carbon-supported honeycomb structure of the present invention has a large amount of activated carbon filled between the fibers of inorganic fiber paper with a high porosity as described above. Compared to the human body, large objects that are impossible to manufacture can be easily manufactured. In addition, while the ratio of activated carbon amount to adsorption amount is 300:50 in the extruded product, the present invention
136:40, and the adsorption capacity is high considering the amount of activated carbon. Further, since activation treatment after forming into a bulky honeycomb structure is not necessary, it is not only possible to manufacture the honeycomb structure at low cost, but also to easily obtain a product with good dimensional accuracy. Furthermore, since the skeleton is made of inorganic fibers, dimensional changes due to humidity are small, and chemical resistance and durability are also good. When comparing the present invention with a conventional honeycomb structure made of paper containing activated carbon, the maximum amount of activated carbon carried in the conventional method is about 65 g/paper volume, whereas in the present invention, the maximum amount of activated carbon supported is about 65 g/paper volume. The amount of adsorption of benzene, alcohol, etc. is 23 mg/ for the conventional product, but the amount of adsorption of benzene, alcohol, etc. is 40 mg/or more, which is about twice as much. In addition, the ozone decomposition efficiency after 80 hours is 72%, compared to 48% for the conventional method, showing excellent decomposition performance. Furthermore, when straining activated carbon, conventionally the loss of expensive activated carbon during the papermaking process is unavoidable, but in the manufacturing method of the present invention in which activated carbon is filled after papermaking, there is almost no loss of activated carbon. Another advantage of the present invention is that the supported activated carbon is not limited by paper-forming properties, extrusion moldability, etc., and there is a high degree of freedom in selecting its type and properties. Furthermore, activated carbon and flame retardant carriers exhibit a high degree of flame retardancy, partly because the skeleton is made of inorganic fibers. Taking advantage of the above-mentioned characteristics, the honeycomb structure of the present invention can be effectively used, for example, in ozone decomposition filters for electronic copying machines and other equipment, filters for various deodorizing agents, catalyst supports, and the like. <<Example>> Examples of the present invention will be described below. However, the present invention is not limited to the following examples. Example 1 Using E glass fiber (fiber diameter 9 μm, fiber length 8 mm), the thickness was 0.2 mm and the inter-fiber void ratio was 94% by a conventional method.
Activated carbon with a particle size of 5 to 40 μm and a specific surface area of 1300 m ² /g (adsorption amount 1170 mg / g) is added to this paper.
A suspension containing an acrylic binder in an amount of 1/10 of the weight of activated carbon was applied and then dried. Obtained activated carbon-filled paper (activated carbon filling amount 136g/
A part of the paper (volume, weight 90g/m ² ) was corrugated. Then, as shown in Figure 1, corrugated paper 1 and unprocessed flat paper 2 are stacked alternately and bonded at the contact points with an acrylic binder containing a thickener.
A honeycomb structure shown in FIG. 2 was obtained. The pitch (cell width) of this honeycomb structure is 3.2
mm, cell height was 1.2 mm, and aperture ratio was 63%. The ozone decomposition performance of the activated carbon supported honeycomb structure obtained by the above method was investigated under the following conditions. Ventilation wind speed: 1.0 m/Sec Ventilation ozone concentration: 1.2 ppm Honeycomb structure thickness in ventilation direction: 20 mm The results are shown in Figure 3. Comparative Example For comparison, an activated carbon-supported honeycomb structure with the same dimensions as above (activated carbon amount 65g/
) was also tested in a similar manner. The results are also shown in FIG. Example 2 In an example of manufacturing a honeycomb structure similar to Example 1, the weight of activated carbon was added to the activated carbon-containing slurry for coating.
A flame retardant consisting of 10% organic phosphorus-containing nitrogen compound was added. The obtained activated carbon-supported honeycomb structure naturally exhibited a high degree of flame retardancy. Further, the same test as in Example 1 was also conducted on this honeycomb structure. The results are also shown in FIG. As is clear from the figure, Examples 1 and 2
The ozone decomposition rate of the honeycomb structure of the present invention, shown in , is almost the same in the initial state as compared to the comparative example, but the decreasing gradient of the adsorption capacity for organic solvents such as benzene with the passage of treatment time is small, and it is sustainable. It has been found that it has a significant effect. Further, the following table shows a comparison of the characteristics of a conventional extruded body, a honeycomb structure formed by paper-making organic fibers, and a honeycomb structure of the present invention.

【表】この表からも明らかなように本発明の製品は、
押出成形体と、有機繊維を抄造したものとの中間
程度以上の性能があり、活性炭量の割りには吸着
能が高くより効率的な性能を示している。[Table] As is clear from this table, the products of the present invention are
It has a performance that is at least intermediate between an extrusion molded product and a paper-made product made from organic fibers, and has a high adsorption capacity and more efficient performance considering the amount of activated carbon.

[Brief explanation of the drawing]

第１図は本発明のハニカム構造体の積層構造を
示す側面図、第２図は同上ハニカム構造体の斜視
図、第３図は実施例製品および比較例のオゾン分
解率の試験結果を示すグラフである。１……活性炭充填無機繊維製紙（コルゲート
紙）、２……活性炭充填無機繊維製紙（無加工平
紙）。 Fig. 1 is a side view showing the laminated structure of the honeycomb structure of the present invention, Fig. 2 is a perspective view of the same honeycomb structure, and Fig. 3 is a graph showing the test results of the ozone decomposition rate of the example product and the comparative example. It is. 1... Activated carbon-filled inorganic fiber paper (corrugated paper), 2... Activated carbon-filled inorganic fiber paper (unprocessed plain paper).

Claims

[Claims] 1. A paper made of high porosity inorganic fibers with a fiber vacancy of 85 to 95%, and activated carbon filled and fixed between the fibers of the paper at a rate of 120 to 150 g/. Honeycomb structure supporting activated carbon. 2 Finely powdered activated carbon and 1/9 of the weight of this activated carbon
Inorganic fiber paper with a fiber void ratio of 85 to 95% is immersed in a suspension of a binder selected from ~1/10 of an acrylic binder, a vinylidene chloride binder, and colloidal silica, or By applying the suspension to inorganic fiber paper and drying it,
Activated carbon is filled between the fibers of the paper at a rate of 120 to 150 g/paper, and the activated carbon-filled paper and the corrugated paper are alternately stacked and bonded, and a predetermined opening is formed in the ventilation direction. 1. A method for producing an activated carbon-supported honeycomb structure, the method comprising forming a honeycomb structure with a high carbon content.