JP3643920B2 - Production method of plate-like activated carbon - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、活性炭を利用するあらゆる分野に適用できる板状活性炭の製造方法に関する。
【０００２】
【従来の技術】
従来、活性炭を利用する技術において実際に用いられている活性炭の形態は、破砕物やペレットなどの粒状活性炭、粉末活性炭、繊維状活性炭、押出し成形活性炭、抄造成形活性炭等である。
【０００３】
【発明が解決しようとする課題】
活性炭はあらゆる物質の吸着性に優れ、気体や液体中の有害物質除去や気体や液体の精製等に用いられており、従来、活性炭の高性能化には様々な工夫が施されている。
【０００４】
一般に、吸着速度の向上には被吸着物質の吸着活性面への拡散速度を向上させることが必要である。この観点から、粒状活性炭よりも粉末活性炭や繊維状活性炭の方が、粒径が小さく従って拡散距離が短いため、吸着速度面で有利であるといえる。しかし、粉末活性炭や繊維状活性炭を気体または液体が連続的に流れる流通系で固定床として用いるのは困難であり、これらを流動床或いはバッチ方式や閉鎖系などで懸濁状態で用いる場合でも、最終的には何らかの形で活性炭を流通系から分離回収する方策を講ずる必要がある。
【０００５】
そこで、気体や液体との分離が簡単で固定床として充填でき、粒状活性炭より拡散速度を向上させることができる活性炭形態として板状の押出し成形活性炭ないしは抄造成形活性炭が開発されている。
【０００６】
押出し成形活性炭は、粉末活性炭や繊維状活性炭を接着成分と混練し、混練物をプレート状或いはプレートの集合体とも言えるハニカム状に押出し成形したものである。また、抄造成形活性炭は、粉末活性炭や繊維状活性炭を接着成分および補強材としての繊維質と共に混練し、混練物を抄造しシート化したものである。
【０００７】
一般に、板状物は、粒状物に比べ、内部への物質拡散距離が短く、また気体ないしは液体との幾何学的な接触面積が広いので、吸着速度面で有利である上に、粒子を充填するより圧力損失の少ない固定床として用いることができる。
【０００８】
しかしながら、押出し成形活性炭や抄造成形活性炭には、下記のような問題点がある。
【０００９】
まず、押出し成形活性炭および抄造成形活性炭はいずれも、殆どの場合、原料の粉末活性炭や繊維状活性炭と同等の性能を示さない。これは、恐らく加工過程での様々な処理により、添加物質による被毒など活性炭自体の変質が起こるであろうし、また粉末活性炭や繊維状活性炭に多量の接着成分や補強剤を添加して全体を混練するため、これら添加成分による活性炭の粒子や繊維の表面近傍での拡散抵抗が高まることが避けられないためである。
【００１０】
また、押出し成形活性炭や抄造成形活性炭の製造には押出し成形設備や抄造設備など何れも大掛かりな専用設備が必要であり、多大な製造コストがかかる。前述したように活性炭の用途は広いため、用途により最適な活性炭の種類や形状を選定する必要があるが、このように大掛かりな専用設備では、製品活性炭の種類によって異なる成形条件、抄造条件並びに原料活性炭の種類などを１ラインで適宜切り換えることが困難であり、また多ラインを設けることも困難であり、あらゆる製品仕様への対応は不可能である。
【００１１】
以上のように、吸着剤として理想的な形状であるとされる押出し成形活性炭や抄造成形活性炭でさえ、期待の性能を発揮できず、しかも高価であり、粒状活性炭のような品揃えができないのが現状である。
【００１２】
本発明の目的は、押出し成形活性炭や抄造成形活性炭のような板状の活性炭を安価にしかも活性炭の性能を損なわないで製造することができる方法を提供することにある。
【００１３】
【課題を解決するための手段】
本発明による板状活性炭の製造方法は、粉末活性炭を両親媒性物質の水溶液または分散液と混合し、得られたスラリーを不燃性プレフォーム体に含浸した後、該プレフォーム体を乾燥または焼成した後、還元または不活性雰囲気で賦活処理する。
両親媒性物質は、ポリビニルアルコールまたはリグニンスルホン酸カルシウムのようなリグニンである。
【００１４】
両親媒性物質がポリビニルアルコールである場合、粉末活性炭をポリビニルアルコールの０．５〜１０重量％、望ましくは１〜５重量％水溶液と混合し、得られたスラリーを不燃性プレフォーム体に含浸した後、該プレフォーム体を空気中で８０〜３５０℃、望ましくは２００〜２２０℃で乾燥した後、還元または不活性雰囲気で４５０〜８００℃で賦活処理する。
両親媒性物質がリグニンである場合、粉末活性炭をリグニンの０．５〜５０重量％、望ましくは１〜１０重量％水溶液と混合し、得られたスラリーを不燃性プレフォーム体に含浸した後、該プレフォーム体を空気中で８０〜２５０℃で乾燥し、乾燥後、還元または不活性雰囲気で３５０〜８００℃で賦活処理する。
不燃性プレフォーム体としては、セラミックス繊維のような無機酸化物繊維の集合体よりなるペーパー、不織布、マット、シート、クロスなどのように、空隙を持つ不燃性プレフォーム体が好ましく用いられる。特に、セラミックスペーパー、または、用途により最適な形状に加工されたセラミックスペーパー加工品が好ましい。
炭素は疎水性であるので水スラリーの状態では炭素粒子間の会合が起こり、スラリー中の炭素粒子は乾燥時の粒径に関係なく大きく、粗めの濾紙などにも捕集される。このことは活性炭がプレプォーム体の表面に溜まり内部の空隙へは浸透しないことを示しており、プレプォーム体を単に水スラリーに浸漬するだけでは活性炭をプレフォーム体の内部に含浸保持させることはできないことが解る。
【００１５】
そこで発明者らは両親媒性を持つ物質を炭素分散剤として活性炭スラリーへ添加することで炭素を微粒化させ、あらゆるプレフォーム体への浸透性スラリーを実現化した。
【００１６】
両親媒性物質はその性質さえあれば基本的に何でも効果はあるが、工程や目的製品のためには以下の条件に合うものが望ましい。
【００１７】
・活性炭粒子を覆わないように、少量で効果があるかまたは乾燥賦活処理過程で分解もしくは炭化して活性炭となりうるもの、
・５００℃以下で上記のような賦活処理ができるもの、
・使用目的に対し毒性を示さないもの。
【００１８】
このような条件を備えた両親媒性物質としては、ポリビニルアルコールまたはリグニンがある。
【００１９】
現在、活性炭は数々の原料、製法によって得られ、様々な特徴を持った製品が多数存在する。本発明による板状活性炭の製造方法には、これら何れの活性炭をも適用できる。
【００２０】
こうして得られた板状活性炭は、粉末活性炭がプレフォーム体繊維間の空隙に繊維質との摩擦力や付着力によって保持されたものである。
【００２１】
本発明には以下のような利点がある。
【００２２】
１．粉末活性炭を、構造を形成するための繊維質や接着剤とは混練せず、主としてプレフォーム体繊維間の空隙に繊維質との摩擦力や付着力によって保持するので、活性炭スラリーに加える接着剤などの添加量は僅かで済み、添加剤による活性炭の性能阻害は殆どないしは全くない。
【００２３】
また、被吸着物質の拡散に必要な粒子間空隙がプレフォーム体繊維間マトリックスによって確保できる。
【００２４】
用途により板状活性炭製品に要求される強度は異なるが、基本的にはプレフォーム体の強度で製品の強度を調整できるので、原料活性炭の種類に左右されない同じ強度の製品が得られる。
【００２５】
２．製造工程はプレフォーム体をスラリー中に浸漬した後引き上げ、乾燥賦活処理するだけのものであるので、浸漬槽と炉があればよく、特別な設備を必要としない。
【００２６】
３．プレフォーム体として、セラミックス繊維のような無機酸化物繊維の集合体よりなるペーパー、不織布、マット、シート、クロスなどから、用途により最適な形状に加工されたものや最適な材質のものを選ぶことができる。
【００２７】
４．異種の板状活性炭へ製造を切り換えるには、浸漬槽のみを変更すれば済み、製造が容易である。こうして用途により最適な原料活性炭を使うことができ、幅広い品揃えが可能である。
【００２８】
５．粉末活性炭がセラミックスペーパーに高分散に保持され、且つ空隙率が高いため、被吸着物質の拡散性がよい。
【００２９】
【発明の実施の形態】
本発明を実施例によって具体的に説明するが、本発明はこれらの実施例に限定させれるものではない。
【００３０】
実施例１
ポリビニルアルコール（平均分子量５００）３．５重量％、粉末活性炭３０重量％、残り水からなる活性炭スラリーを調製し、厚さ０．５ｍｍのセラミックスペーパーに含浸保持させ、１１０℃で乾燥し、４７０℃で窒素雰囲気で賦活処理して、炭素７０（ｇ／ｍ２）を保持した薄板状活性炭を得た。
【００３１】
この薄板状活性炭の表面を擦っても炭素は落ちなかった。
【００３２】
実施例２
リグニンスルホン酸カルシウム４重量％、粉末活性炭３０重量％、残り水からなる活性炭スラリーを調製し、厚さ０．５ｍｍのセラミックスペーパーに含浸保持させ、１１０℃で乾燥し、４００℃で窒素雰囲気で賦活処理して、炭素７０（ｇ／ｍ２）を保持した薄板状活性炭を得た。
【００３３】
この薄板状活性炭の表面を擦っても炭素は落ちなかった。
【００３４】
比較例１
粉末活性炭３０重量％と残り水からなる活性炭スラリーを調製し、これに厚さ０．５ｍｍのセラミックスペーパーを浸漬したところ、水のみがセラミックスペーパー内に浸透し、泥状の高濃度スラリーが表面にへばり付いた。これを１１０℃で乾燥している間に活性炭は自然に粉落ちした。
【００３５】
実施例１および２で得た薄板状活性炭と原料の粉末活性炭の比表面積を表１に示す。
【００３６】
実施例１、２および比較例１のスラリー粘度、ならびに目開き１７７μｍの篩にスラリーを通した時の篩上に残存した活性炭の比率（捕捉率）を表２に示す。
【００３７】
【表１】
【発明の効果】
本発明方法によれば、活性炭をその用途に従って最適な板状形態に加工することができる。また、製造設備としては浸漬槽と炉があればよく、設備費が安価であり、製造も浸漬と賦活処理工程のみで簡便である。しかも、得られた板状活性炭は原料の粉末活性炭の性能を損なわないものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing plate-like activated carbon that can be applied to all fields using activated carbon.
[0002]
[Prior art]
Conventionally, the form of activated carbon actually used in the technology using activated carbon is granular activated carbon such as crushed material and pellets, powdered activated carbon, fibrous activated carbon, extruded activated carbon, and paper-molded activated carbon.
[0003]
[Problems to be solved by the invention]
Activated carbon is excellent in adsorptivity of all substances and is used for removing harmful substances in gases and liquids and purifying gases and liquids. Conventionally, various measures have been taken to improve the performance of activated carbon.
[0004]
Generally, in order to improve the adsorption rate, it is necessary to improve the diffusion rate of the substance to be adsorbed on the adsorption active surface. From this point of view, it can be said that powdered activated carbon and fibrous activated carbon are more advantageous in terms of adsorption speed than granular activated carbon because the particle size is smaller and the diffusion distance is shorter. However, it is difficult to use powdered activated carbon or fibrous activated carbon as a fixed bed in a flow system in which gas or liquid continuously flows, and even when these are used in a suspended state in a fluidized bed or a batch system or a closed system, Eventually, it is necessary to take measures to separate and recover the activated carbon from the distribution system in some form.
[0005]
Accordingly, plate-like extruded activated carbon or paper-molded activated carbon has been developed as an activated carbon form that can be easily separated from gas and liquid, can be filled as a fixed bed, and can improve the diffusion rate over granular activated carbon.
[0006]
Extruded activated carbon is obtained by kneading powdered activated carbon or fibrous activated carbon with an adhesive component, and extruding the kneaded product into a honeycomb shape that can be said to be a plate or an aggregate of plates. The paper-molded activated carbon is obtained by kneading powdered activated carbon or fibrous activated carbon together with an adhesive component and a fiber as a reinforcing material, and paper-making the kneaded product.
[0007]
In general, a plate-like material has a shorter material diffusion distance to the inside than a granular material and has a wide geometric contact area with a gas or liquid, so it is advantageous in terms of adsorption speed and packed with particles. Therefore, it can be used as a fixed bed with less pressure loss.
[0008]
However, extrusion-molded activated carbon and paper-molded molded activated carbon have the following problems.
[0009]
First, both extruded and activated carbons do not exhibit the same performance as raw material powdered activated carbon or fibrous activated carbon. This is probably due to various treatments in the processing process, which may cause alteration of the activated carbon itself, such as poisoning due to additive substances, and adding a large amount of adhesive components and reinforcing agents to powdered activated carbon and fibrous activated carbon. This is because kneading causes an increase in diffusion resistance in the vicinity of the activated carbon particles and fibers due to these additive components.
[0010]
Also, the production of extruded activated carbon and paper-molded activated carbon requires large dedicated equipment such as extrusion molding equipment and paper-making equipment, which requires a large production cost. As described above, since activated carbon has a wide range of applications, it is necessary to select the most appropriate activated carbon type and shape depending on the application, but in such a large dedicated facility, the molding conditions, papermaking conditions and raw materials differ depending on the type of activated carbon. It is difficult to appropriately switch the type of activated carbon in one line, and it is also difficult to provide multiple lines, making it impossible to meet all product specifications.
[0011]
As described above, even extruded activated carbon and paper-molded activated carbon, which are considered to be ideal shapes as adsorbents, cannot exhibit the expected performance, are expensive, and cannot be assorted as granular activated carbon. Is the current situation.
[0012]
An object of the present invention is to provide a method capable of producing plate-like activated carbon such as extrusion-molded activated carbon and paper-molded activated carbon at a low cost and without impairing the performance of the activated carbon.
[0013]
[Means for Solving the Problems]
In the method for producing plate-like activated carbon according to the present invention, powdered activated carbon is mixed with an aqueous solution or dispersion of an amphiphilic substance, and the resulting slurry is impregnated into an incombustible preform, and then the preform is dried or calcined. After that, activation treatment is performed in a reducing or inert atmosphere.
Amphiphiles, lignin, such as port polyvinyl alcohol or calcium lignosulfonate.
[0014]
When the amphiphilic substance is polyvinyl alcohol, powdered activated carbon is mixed with an aqueous solution of 0.5 to 10% by weight of polyvinyl alcohol, preferably 1 to 5% by weight, and the resulting slurry is impregnated into a nonflammable preform. after, 80 to 350 ° C. in air the preforms, preferably after drying at 200 to 220 ° C., activation treatment at 450 to 800 ° C. in a reducing or inert atmosphere.
When the amphiphile is lignin, powdered activated carbon is mixed with an aqueous solution of 0.5 to 50% by weight of lignin, preferably 1 to 10% by weight, and after impregnating the resulting slurry into a nonflammable preform body, the preforms were dried at 80 to 250 ° C. in air, dry燥後, activation treatment under reducing or 350 to 800 ° C. in an inert atmosphere.
As the non-combustible preform body, a non-combustible preform body having a void such as a paper, a nonwoven fabric, a mat, a sheet, a cloth made of an aggregate of inorganic oxide fibers such as ceramic fibers is preferably used. In particular, ceramic paper or a processed ceramic paper processed into an optimum shape depending on the application is preferable.
Since carbon is hydrophobic, association between carbon particles occurs in a water slurry state, and the carbon particles in the slurry are large regardless of the particle size at the time of drying, and are also collected on coarse filter paper or the like. This indicates that the activated carbon accumulates on the surface of the preform body and does not penetrate into the voids inside, and the activated carbon cannot be impregnated and retained inside the preform body simply by immersing the preform body in the water slurry. I understand.
[0015]
Accordingly, the inventors have added amphiphilic substances as carbon dispersants to the activated carbon slurry to atomize the carbon and realize a permeable slurry for all preform bodies.
[0016]
Amphiphiles are basically effective insofar as their properties are met, but those that meet the following conditions are desirable for the process and target product.
[0017]
・ Effective in a small amount so as not to cover the activated carbon particles, or can be activated or carbonized by decomposition or carbonization during the drying activation process,
-What can be activated as described above at 500 ° C or lower,
・ Does not show toxicity for intended use
[0018]
The amphiphiles having such conditions, there is a port polyvinyl alcohol or lignin.
[0019]
At present, activated carbon is obtained by various raw materials and manufacturing methods, and there are many products with various characteristics. Any of these activated carbons can be applied to the method for producing plate-like activated carbon according to the present invention.
[0020]
In the plate-like activated carbon thus obtained, powdered activated carbon is held in the gaps between the preform body fibers by the frictional force and adhesion with the fiber.
[0021]
The present invention has the following advantages.
[0022]
1. Adhesive added to activated carbon slurry because powdered activated carbon is not kneaded with fibers and adhesives to form the structure, but is mainly retained in the gaps between the preform body fibers by friction and adhesion with the fibers. The amount of addition such as is small, and there is little or no inhibition of the performance of the activated carbon by the additive.
[0023]
Also, the interparticle voids necessary for the diffusion of the adsorbed substance can be secured by the preform body interfiber matrix.
[0024]
The strength required for the plate-like activated carbon product differs depending on the use, but basically, the strength of the product can be adjusted by the strength of the preform, so that a product having the same strength regardless of the type of the activated carbon can be obtained.
[0025]
2. Since the manufacturing process involves only immersing the preform body in the slurry and then pulling it up and subjecting it to a dry activation treatment, it is sufficient to have a dipping tank and a furnace, and no special equipment is required.
[0026]
3. Select a preform that has been processed into an optimal shape or material from the paper, nonwoven fabric, mat, sheet, cloth, etc. made of an aggregate of inorganic oxide fibers such as ceramic fibers. Can do.
[0027]
4). In order to switch the production to a different type of plate-like activated carbon, it is only necessary to change the immersion tank, and the production is easy. In this way, the most suitable raw material activated carbon can be used depending on the application, and a wide range of products is possible.
[0028]
5. Since the powdered activated carbon is highly dispersed in the ceramic paper and has a high porosity, the diffusibility of the adsorbed substance is good.
[0029]
DETAILED DESCRIPTION OF THE INVENTION
EXAMPLES The present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
[0030]
Example 1
An activated carbon slurry consisting of 3.5% by weight of polyvinyl alcohol (average molecular weight 500), 30% by weight of powdered activated carbon and the remaining water is prepared, impregnated and held in a ceramic paper having a thickness of 0.5 mm, dried at 110 ° C., and 470 ° C. Then, activation treatment was performed in a nitrogen atmosphere to obtain a thin plate-like activated carbon retaining carbon 70 (g / m 2 ).
[0031]
Even when the surface of the thin plate-like activated carbon was rubbed, carbon did not fall.
[0032]
Example 2
An activated carbon slurry consisting of 4% by weight of calcium lignin sulfonate, 30% by weight of powdered activated carbon and the remaining water is prepared, impregnated and held in a ceramic paper having a thickness of 0.5 mm, dried at 110 ° C., and activated in a nitrogen atmosphere at 400 ° C. By processing, a thin plate-like activated carbon retaining carbon 70 (g / m 2 ) was obtained.
[0033]
Even when the surface of the thin plate-like activated carbon was rubbed, carbon did not fall.
[0034]
Comparative Example 1
An activated carbon slurry consisting of 30% by weight of powdered activated carbon and the remaining water was prepared. When ceramic paper with a thickness of 0.5 mm was immersed in this, only water penetrated into the ceramic paper, and a mud-like high-concentration slurry was formed on the surface. I was stuck. While this was dried at 110 ° C., the activated carbon naturally fell off.
[0035]
Table 1 shows the specific surface areas of the thin plate-like activated carbon obtained in Examples 1 and 2 and the raw material powdered activated carbon.
[0036]
Table 2 shows the slurry viscosities of Examples 1 and 2 and Comparative Example 1, and the ratio (capture rate) of activated carbon remaining on the sieve when the slurry was passed through a sieve having an opening of 177 μm.
[0037]
[Table 1]
【The invention's effect】
According to the method of the present invention, activated carbon can be processed into an optimal plate form according to its use. Further, the manufacturing equipment may be an immersion tank and a furnace, the equipment cost is low, and the manufacturing is simple only by the immersion and activation treatment steps. Moreover, the obtained plate-like activated carbon does not impair the performance of the raw powder activated carbon.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29515197A JP3643920B2 (en) | 1997-10-28 | 1997-10-28 | Production method of plate-like activated carbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29515197A JP3643920B2 (en) | 1997-10-28 | 1997-10-28 | Production method of plate-like activated carbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11130415A JPH11130415A (en) | 1999-05-18 |
| JP3643920B2 true JP3643920B2 (en) | 2005-04-27 |
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| JP29515197A Expired - Fee Related JP3643920B2 (en) | 1997-10-28 | 1997-10-28 | Production method of plate-like activated carbon |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100387990B1 (en) * | 2000-10-27 | 2003-06-18 | 김철갑 | Method of making activated carbons using pulp sludges containing lignin produced as by products when making corncob pulp |
| US20060247121A1 (en) * | 2003-02-17 | 2006-11-02 | Jong-Seob Shim | Manufacturing method of activated carbon structure having a frame |
| KR100509348B1 (en) * | 2003-02-17 | 2005-08-22 | 심종섭 | A manufacturing method of activated carbon structure having a frame |
| US20050014002A1 (en) * | 2003-07-15 | 2005-01-20 | Ramesh Varadaraj | Lignin-solids compositions |
| JP5013503B2 (en) * | 2006-02-16 | 2012-08-29 | 国立大学法人埼玉大学 | Method for producing hydrophobic activated carbon |
| NO3131848T3 (en) * | 2014-04-14 | 2018-08-25 |
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| JPH11130415A (en) | 1999-05-18 |
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