JPH03146722A - Production of activated carbon composed of spherical fiber lump - Google Patents
Production of activated carbon composed of spherical fiber lumpInfo
- Publication number
- JPH03146722A JPH03146722A JP1277157A JP27715789A JPH03146722A JP H03146722 A JPH03146722 A JP H03146722A JP 1277157 A JP1277157 A JP 1277157A JP 27715789 A JP27715789 A JP 27715789A JP H03146722 A JPH03146722 A JP H03146722A
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- pitch
- spinning
- spherical
- fiber
- 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.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000000835 fiber Substances 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000011295 pitch Substances 0.000 claims abstract description 24
- 238000009987 spinning Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000011271 tar pitch Substances 0.000 claims abstract description 7
- 238000002074 melt spinning Methods 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 230000004913 activation Effects 0.000 claims description 19
- 238000001179 sorption measurement Methods 0.000 abstract description 14
- 230000003213 activating effect Effects 0.000 abstract description 3
- 238000003795 desorption Methods 0.000 abstract description 3
- 238000001994 activation Methods 0.000 description 19
- 239000007789 gas Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 239000011148 porous material Substances 0.000 description 12
- 230000007423 decrease Effects 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000008901 benefit Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- 238000002336 sorption--desorption measurement Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000011949 advanced processing technology Methods 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000011294 coal tar pitch Substances 0.000 description 2
- 238000004332 deodorization Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000010035 extrusion spinning Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
Landscapes
- Nonwoven Fabrics (AREA)
- Carbon And Carbon Compounds (AREA)
- Inorganic Fibers (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はタールピッチを原料として、公害防止および環
境浄化、食品工業、石油工業等に用いられる高度処理技
術に不可欠な高機能性繊維状活性炭を製造する方法に関
するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention uses tar pitch as a raw material to produce highly functional fibrous activated carbon, which is essential for advanced processing technology used in pollution prevention and environmental purification, the food industry, the petroleum industry, etc. The present invention relates to a method for manufacturing.
（従来の技術）
活性炭は無数の微細孔を有し、単位重量当りの外表面積
が大きく、気相、液相中での種々の分子を吸着、保持し
、また脱離させることもできるという機能を有している
。従って、従来から活性炭は、この吸着脱離能力を活か
して種々の分子の分離剤、除去剤、吸着剤、分解剤、回
収剤、触媒、触媒担体等として用いられている。(Prior art) Activated carbon has countless micropores, has a large outer surface area per unit weight, and has the ability to adsorb, retain, and desorb various molecules in the gas and liquid phases. have. Therefore, activated carbon has conventionally been used as a separation agent, removal agent, adsorbent, decomposition agent, recovery agent, catalyst, catalyst carrier, etc. for various molecules by taking advantage of its adsorption/desorption ability.
（発明が解決しようとする課題）
活性炭は、その形態から、一般に粒径が１４９μｍ以下
の粉末活性炭と、粒径が１ｍｍ〜３ｍｍ程度の粒状活性
炭と、無定形の繊維状活性炭とに大別される。ここで、
粉末活性炭は、粒状活性炭に比べて、単位重量当りの外
表面積が大きく、吸着速度が速いという利点はあるが、
粒径が１４９μｍ以下と小さいために飛散し易く、概し
て取扱いが困難で、粉塵爆発の危険性を有している。ま
た、固定層で使用するとき通気抵抗が大きいことから、
気相中での使用は困難であり、処理液と適当量の活性炭
を混合した後に濾過する接触回分法で利用され、一般に
は、液相中での種々の分子の分離剤、除去剤、吸着剤、
分解剤、回収剤、触媒担体としてしか用いられないとい
う欠点を有している。仮に、気相中で、有害物質の種々
の分子の吸着効果を得ようとすれば、処理量の減少、い
わゆる吸着効率の低下を招くことになり、好ましくない
。(Problems to be Solved by the Invention) Activated carbon is generally classified into powdered activated carbon with a particle size of 149 μm or less, granular activated carbon with a particle size of about 1 mm to 3 mm, and amorphous fibrous activated carbon based on its form. Ru. here,
Powdered activated carbon has the advantage of having a larger outer surface area per unit weight and faster adsorption speed than granular activated carbon.
Because the particle size is as small as 149 μm or less, it easily scatters, is generally difficult to handle, and poses a risk of dust explosion. In addition, since the ventilation resistance is large when used in a fixed layer,
It is difficult to use in the gas phase, so it is used in a contact batch method in which the treatment liquid is mixed with an appropriate amount of activated carbon and then filtered.Generally, it is used as a separation agent, removal agent, or adsorption agent for various molecules in the liquid phase. agent,
It has the disadvantage that it can only be used as a decomposer, a recovery agent, and a catalyst carrier. If an attempt is made to obtain the effect of adsorbing various molecules of harmful substances in the gas phase, this is not preferable because it will result in a decrease in the throughput, or a so-called decrease in adsorption efficiency.
一方、粒状活性炭は、粉末活性炭に比べて取扱い易く、
飛散しにくく、粉塵爆発の危険性もなく、また固定層で
使用するときは通気抵抗が小さいことから、気相中でも
液相中でも利用でき、さらに再生使用ができるという利
点を有するが、破砕粉化されやすく、単位重量当りの外
表面積が小さく、吸着速度、脱着速度が遅いという欠点
も有している。従って、仮に、精製しようとするガスま
たは液を粒状活性炭層に流し、低濃度の有害物の種々の
分子を十分に吸着除去しようとすると、大容量の粒状活
性炭層を必要とし、処理量の減少、いわゆる吸着効率の
低下を招く結果となる。また、精製しようとするガスま
たは液を粒状活性炭流動層に流し、有害物質の種々の分
子を吸着除去しようとすれば、粒径が１〜３ｍｍ程度と
大きいことや粒子密度が大きいことから、多量のガスま
たは液流を必要とし、吸着除去率の低下を招き、粒状活
性炭の摩耗、破砕ロスを引き起こすことになる。On the other hand, granular activated carbon is easier to handle than powdered activated carbon.
It is difficult to scatter, there is no risk of dust explosion, and when used in a fixed bed, the ventilation resistance is small, so it can be used in both gas and liquid phases, and it has the advantage of being recyclable. They also have the disadvantages of being easily absorbed, having a small external surface area per unit weight, and having slow adsorption and desorption rates. Therefore, if the gas or liquid to be purified were to be passed through a granular activated carbon layer to sufficiently adsorb and remove various molecules of harmful substances at low concentrations, a large capacity granular activated carbon layer would be required, resulting in a reduction in the throughput. This results in a so-called decrease in adsorption efficiency. In addition, if the gas or liquid to be purified is passed through a granular activated carbon fluidized bed to adsorb and remove various molecules of harmful substances, a large amount of particles will be generated due to the large particle size of about 1 to 3 mm and the high particle density. This requires a gas or liquid flow of 100%, which leads to a decrease in the adsorption removal rate and causes abrasion of the granular activated carbon and crushing loss.
これらに対し、繊維状活性炭は、一般に炭素繊維をガス
賦活または薬品賦活することで製造される繊維状の活性
炭で、単位重量当りの外表面積が大きく、吸着脱着速度
が速いという利点はあるが、それ自体の繊維集合体とし
ての強度、形状維持性が悪く、飛散し易いために作業性
、取扱い性も悪い。また、空隙率が高く、充填密度が低
いという欠点も有している。さらに、再生処理、再使用
に当たっても、飛散し易いこと、形状維持性が悪いこと
から、空隙率、充填密度の再現性が悪いという問題があ
る。従って、仮に、精製しようとするガスまたは液を、
繊維状活性炭を綿状に充填した繊維状活性炭層に流し、
有害物質の種々の分子を十分に除去しようとすると、大
容量の繊維状活性炭層を必要とし、経済的でなく、処理
量の減少、いわゆる吸着効率の低下を招く結果となる。On the other hand, fibrous activated carbon is generally produced by activating carbon fibers with gas or chemicals, and has the advantage of having a large outer surface area per unit weight and a fast adsorption/desorption rate. As a fiber aggregate itself, it has poor strength and shape retention, and is easily scattered, resulting in poor workability and handling. It also has the disadvantages of high porosity and low packing density. Furthermore, even when recycled or reused, there is a problem that the reproducibility of porosity and packing density is poor because it is easy to scatter and has poor shape retention. Therefore, if the gas or liquid to be purified is
The fibrous activated carbon is poured into a fibrous activated carbon layer filled with cotton.
In order to sufficiently remove various molecules of harmful substances, a large-capacity fibrous activated carbon layer is required, which is not economical and results in a decrease in throughput, so-called a decrease in adsorption efficiency.
また、精製しようとするガスまたは液を、繊維状活性炭
を綿状に充填した繊維状活性炭流動層に流し有害物の種
々の分子の吸着除去を行うとすると綿状にした繊維体は
形状維持性が悪く、ばらけ飛散し、摩耗、破砕ロスを引
起こし、同じく吸着除去率の低下、処理量の減少、いわ
ゆる吸着効率の低下を招くことになる。さらに、この形
状維持性を改善する目的で織物、不織布、フェルト、マ
ット、ペーパー等に加工し利用するには、強度をもたせ
るための混紡繊維を必要とし、加工費がかかり経済的で
ないばかりか、加工品では、活性炭素繊維の含有率が低
くなるため単位重量当りの外表面積が低下するという問
題がある。また一般に行われている活性炭再生炉による
熱再生法が困難となり、再生使用ができなくなるという
問題も出てくる。In addition, if the gas or liquid to be purified is passed through a fibrous activated carbon fluidized bed filled with fibrous activated carbon to adsorb and remove various molecules of harmful substances, the floc-like fibrous body will not maintain its shape. This results in poor adsorption and scattering, causing abrasion and crushing loss, which also leads to a decrease in adsorption removal rate, a decrease in throughput, and a decrease in so-called adsorption efficiency. Furthermore, in order to process and use fabrics, non-woven fabrics, felts, mats, papers, etc. for the purpose of improving shape retention, blended fibers are required to provide strength, which not only increases processing costs but is also uneconomical. In processed products, there is a problem in that the outer surface area per unit weight decreases due to the lower content of activated carbon fibers. Further, the problem arises that the commonly used heat regeneration method using an activated carbon regeneration furnace becomes difficult, and reuse becomes impossible.
一方、近年、トリクロロエチレン等による地下水の汚染
問題の対策、水道水のトリへロメタン対策、フロンガス
対策、脱臭、消臭、快適さなど、アメニティ−空間の創
造等の社会的な盛り上がりを背景に、活性炭の機能性の
向上、形状の改良が求められている。On the other hand, in recent years, against the backdrop of social upsurge in the creation of amenity-spaces, such as countermeasures against groundwater contamination by trichlorethylene, countermeasures against trichloromethane in tap water, countermeasures against fluorocarbon gas, deodorization, deodorization, comfort, etc., activated carbon is being used. Improvements in functionality and shape are required.
そこで、本発明の目的は、上述したような従来の活性炭
、すなわち、粉状活性炭、粒状活性炭、および繊維状活
性炭の欠点を解消し、吸着力が高く、吸着脱着速度が速
く、ハンドリング性が良好で形状維持性が良（、かつ再
生使用が容易な高機能性な球状活性炭素繊維の製造方法
を提供することにある。SUMMARY OF THE INVENTION Therefore, the purpose of the present invention is to eliminate the drawbacks of the conventional activated carbon, that is, powdered activated carbon, granular activated carbon, and fibrous activated carbon, as described above, and have high adsorption power, fast adsorption/desorption rate, and good handling properties. The purpose of the present invention is to provide a method for producing highly functional spherical activated carbon fibers that have good shape retention (and are easy to reuse).
（課題を解決するための手段）
本発明者らは、上記課題を解決すべく鋭意検討を行った
結果、タールピッチを原料として紡糸した後に、このピ
ッチ繊維に球状化処理を施して球状ピッチ繊維塊を得、
これを不融化、さらに賦活化することにより、高機能性
の球状活性炭素繊維が得られることを見出し、本発明を
完成するに至った。(Means for Solving the Problems) As a result of intensive studies to solve the above problems, the present inventors have found that after spinning tar pitch as a raw material, the pitch fibers are subjected to a spheroidization treatment to form spherical pitch fibers. get a lump,
It was discovered that a highly functional spherical activated carbon fiber could be obtained by making it infusible and further activating it, and the present invention was completed.
すなわち、本発明は、タールピッチを原料として紡糸用
ピンチを調製し、この紡糸用ピッチを溶融紡糸した後、
球状化処理を施し、次いで酸化性雰囲気で不融化し、さ
らに賦活化処理することを特徴とする球状繊維塊活性炭
の製造方法に関するものである。That is, the present invention prepares a spinning pinch using tar pitch as a raw material, and after melt-spinning this spinning pitch,
The present invention relates to a method for producing activated carbon made of spherical fiber aggregates, which is characterized by performing a spheroidizing treatment, then infusible in an oxidizing atmosphere, and further performing an activation treatment.
（作 用）
以下、本発明の球状繊維塊活性炭の製造方法を詳細に説
明する。(Function) Hereinafter, the method for producing the spherical fiber aggregate activated carbon of the present invention will be explained in detail.
本発明に用いる原料はタールピッチとする。これは、従
来製造されているポリアクリロニトリル系、フェノール
樹脂系、セルロース系等に比べて、クールピッチを原料
としたほうが、原料が安価であり、かつ賦活化収率が高
いからである。また、ここで用いるクールピッチは、後
工程の紡糸、不融化、炭化に適したものとなるように適
度に重質化された高軟化点のものが適しており、２００
’Ｃ以上の軟化点のものが好ましい。このようなピッチ
の製造方法としては、例えば特公昭６１−００２７１２
号公報などに提案されているように、精製、溶剤抽出、
蒸留、熱処理などを施して調製されたものが適している
。The raw material used in the present invention is tar pitch. This is because using cool pitch as a raw material is cheaper and has a higher activation yield than conventionally produced polyacrylonitrile-based, phenolic resin-based, cellulose-based, etc. In addition, the cool pitch used here is suitably heavy and has a high softening point so that it is suitable for spinning, infusibility, and carbonization in the subsequent steps, and is suitable for
Those with a softening point of 'C or higher are preferred. As a method for manufacturing such a pitch, for example, Japanese Patent Publication No. 61-002712
Purification, solvent extraction,
Those prepared by distillation, heat treatment, etc. are suitable.
ピッチの紡糸は、公知の方法により行うことができ、例
えば溶融押出紡糸、遠心紡糸等の方法を採用することが
できる。Pitch spinning can be performed by a known method, such as melt extrusion spinning or centrifugal spinning.
次に、ピッチ繊維を球状化するが、この方法としては、
例えば内部に旋回気流を生じさせた円筒容器中に炭素繊
維の短繊維集合体を混入し気流とともに旋回させる方法
が提案されており （特開昭６２−１１４６３６号公報
）、本発明においてもこの方法を利用することができる
。Next, the pitch fibers are spheroidized, but this method is as follows:
For example, a method has been proposed in which short carbon fiber aggregates are mixed in a cylindrical container with a swirling airflow inside and swirled together with the airflow (Japanese Patent Application Laid-Open No. 114636/1983), and this method is also used in the present invention. can be used.
次いで、不融化工程では、得られた球状ピッチ繊維を高
温で賦活化する際に球状の繊維形状を維持できるように
するため、酸化処理を行い、例えば酸化性の雰囲気下に
て１５０〜３５０″Ｃ程度の温度で行う。このとき、回
分式の不融化炉を用いて不融化することもできるが、本
発明では、繊維を球状に加工しているために、ハンドリ
ング性が良いので、連続式の不融化炉を用いて効率よく
不融化を行なうことができる。さらに、本発明の有利な
点は、上述したように回分式で処理した場合においても
不融化処理した球状の繊維を、引き続き炉内の雰囲気を
賦活化用のガスに切り換えて、さらに昇温し所定の温度
で賦活化処理を行うことができるため、熱損失が少ない
点にある。すなわち、従来の方法では、最終製品を不織
布、フェルト、マット、ペーパー等に加工するために、
不融化処理に続いて、高温での炭化処理を行い加工する
に必要な強度を確保した後、再び賦活化のために再昇温
を行う必要があった。Next, in the infusibility step, in order to maintain the spherical fiber shape when the obtained spherical pitch fibers are activated at a high temperature, an oxidation treatment is performed, for example, in an oxidizing atmosphere to a diameter of 150 to 350". It is carried out at a temperature of about C.At this time, it is also possible to infusible using a batch type infusibility furnace, but in the present invention, since the fibers are processed into spherical shapes, they are easy to handle, so a continuous type infusibility furnace is used. Furthermore, the advantage of the present invention is that even when the treatment is performed in a batch manner as described above, the spherical fibers that have been made infusible can be continuously treated in the furnace. Since the atmosphere inside the chamber can be switched to an activation gas, the temperature can be raised further, and the activation process can be performed at a predetermined temperature, resulting in less heat loss.In other words, in the conventional method, the final product is , for processing into felt, mat, paper, etc.
Following the infusibility treatment, a high-temperature carbonization treatment was performed to ensure the strength necessary for processing, and then the temperature had to be raised again for activation.
賦活化処理方法としては、通常の水蒸気、炭酸ガス、酸
素、空気等によるガス賦活法を採用することができる。As the activation treatment method, a usual gas activation method using water vapor, carbon dioxide, oxygen, air, etc. can be adopted.
あるいはまた、薬品による賦活化を適用することもでき
る。通常、ガス賦活法では、活性炭素繊維の特性は賦活
化処理の温度、時間等により制御されるが、本発明にお
いても同様にして最終製品となる繊維状活性炭の細孔径
、細孔分布、比表面積を制御することができる。ガス賦
活する場合の好ましい賦活化条件としては、賦活化温度
が７００〜１０００℃で、賦活化時間が０〜２４０分で
ある。しかし、要求される特性に合わせて条件を選択す
る必要がある。すなわち、広い細孔径分布を持ち、かつ
大きい平均細孔半径を有する繊維状活性炭を得るには、
高温で短時間処理するのが好ましく、一方狭い細孔径分
布を持ち、かつ平均細孔半径の小さい繊維状活性炭を得
るには、低温で長時間処理するのが好ましい。また、賦
活化装置としては、回分式、あるいは本発明では繊維が
球状化されているためハンドリング性が良いので連続式
の賦活化炉も採用することもできるが、上述したように
不融化炉と兼用できる公知の装置を適宜選択して利用す
ることが好ましい。Alternatively, chemical activation can also be applied. Normally, in the gas activation method, the characteristics of activated carbon fibers are controlled by the temperature, time, etc. of the activation treatment, but in the present invention, the pore diameter, pore distribution, and ratio of the fibrous activated carbon that becomes the final product are Surface area can be controlled. Preferred activation conditions for gas activation include an activation temperature of 700 to 1000°C and an activation time of 0 to 240 minutes. However, it is necessary to select conditions according to the required characteristics. That is, in order to obtain fibrous activated carbon that has a wide pore size distribution and a large average pore radius,
It is preferable to treat at a high temperature for a short time, whereas in order to obtain a fibrous activated carbon having a narrow pore size distribution and a small average pore radius, it is preferable to treat at a low temperature for a long time. In addition, as the activation device, a batch type or, in the present invention, a continuous type activation furnace can be used since the fibers are spherical and easy to handle, but as mentioned above, a non-fusible type It is preferable to appropriately select and utilize a known device that can be used for both purposes.
以上述べた本発明の製造方法は、生産性良く、かつ熱的
損失が少ない状態で球状繊維塊活性炭を製造することが
できる。The production method of the present invention described above can produce activated carbon spherical fiber aggregates with high productivity and with little thermal loss.
以上のようにして得た球状繊維塊活性炭は、単位重量当
りの外表面積が大きく、吸着脱着速度が速く、しかも球
状であることから、作業性、ハンドリング性に優れ、あ
らゆる形状に充填することが可能で、かつ緻密な充填を
行うことができる。The spherical fibrous activated carbon obtained as described above has a large outer surface area per unit weight, has a fast adsorption/desorption rate, and is spherical, so it has excellent workability and handling, and can be filled into any shape. It is possible to perform dense filling.
また、形状維持性が良いため、再生ロスが少なく、再生
使用が容易である。さらに、高機能性を活かして、液相
、気相を問わず公害防止、環境浄化に用いることができ
る。In addition, since the shape retention property is good, there is little regeneration loss and it is easy to recycle and use. Furthermore, by taking advantage of its high functionality, it can be used for pollution prevention and environmental purification regardless of whether it is in the liquid or gas phase.
（実施例）
夫」自生上
コールタールピッチを濾過精製した後、熱処理してベン
ゼン不溶分（Ｂｌ）５７％、キノリンネ溶分（ＱＩ）痕
跡量のピッチを得た。このピッチの粘度は、２９８°Ｃ
で１００ｐｏｉｓｅを示し、軟化点は２４０°Ｃであっ
た。また、偏光顕微鏡下４００倍で観察したところ、全
面が光学的等方性を示す均質なピッチであった。(Example) Natural coal tar pitch was filtered and purified, and then heat treated to obtain pitch containing 57% benzene insoluble content (Bl) and a trace amount of quinoline soluble content (QI). The viscosity of this pitch is 298°C
It showed 100 poise and the softening point was 240°C. Further, when observed under a polarizing microscope at a magnification of 400 times, the entire surface had a uniform pitch exhibiting optical isotropy.
次に、このピッチで溶融押し出し紡糸を行い、繊維径２
０μｍのピッチ繊維を得、次いでこの繊維を、６ｍｍの
長さに切断しチョップ状にした後、円筒容器に挿入し、
旋回気流を生じさせながら旋回したところ、球状のピッ
チ繊維を得ることができた。Next, melt extrusion spinning is performed at this pitch, and the fiber diameter is 2
A pitch fiber of 0 μm was obtained, and then this fiber was cut into a length of 6 mm into a chop shape, and then inserted into a cylindrical container.
By swirling while generating a swirling airflow, spherical pitch fibers could be obtained.
次いで、この球状ピッチ繊維を回分式の炉を用いて、空
気中３１０″Ｃまで昇温して不融化処理を行い、引続き
炉内に３３％の水蒸気を含む窒素ガスを流通させながら
昇温し、この中で８５０″Ｃで２時間保持することによ
り賦活化処理を行った。Next, this spherical pitch fiber was heated to 310"C in air using a batch type furnace to make it infusible, and then the temperature was raised while nitrogen gas containing 33% water vapor was passed through the furnace. , in which activation treatment was carried out by holding at 850''C for 2 hours.
得られた賦活化繊維の収率は２８％であり、比表面積（
マイクロメリティクス社製、アサツブ２０００を用いて
測定し、ラングミュア法にて解析） ２０２０ｍ Ｚ
／ ｇ、繊維径１４μｍ 、 ｔａ維強度２０ｋｇ／ｍ
−の活性炭素繊維であった。また、平均細孔径が１７入
、ｔ−プロット法による細孔径１０Å以下の容積率が６
０％であった。The yield of the obtained activated fibers was 28%, and the specific surface area (
Measured using Asatsubu 2000 manufactured by Micromeritics and analyzed using Langmuir method) 2020m Z
/g, fiber diameter 14μm, TA fiber strength 20kg/m
- activated carbon fiber. In addition, the average pore diameter is 17, and the volume fraction with pore diameters of 10 Å or less according to the t-plot method is 6.
It was 0%.
夫」叫」呈
実施例１で得た球状ピッチ繊維を回分式の炉を用いて、
空気中３１０°Ｃまで昇温して不融化を行った後、引続
き雰囲気中に３３％の水蒸気を含む窒素ガスを流通させ
て昇温し、この中で８００″Ｃで２時間保持することに
より賦活化処理を行った。The spherical pitch fibers obtained in Example 1 were heated in a batch furnace.
After making it infusible by raising the temperature to 310°C in air, the temperature was raised by passing nitrogen gas containing 33% water vapor into the atmosphere, and the temperature was kept at 800°C for 2 hours. Activation treatment was performed.
得られた賦活化繊維の収率は５３％であり、比表面積１
４８０ｍ”／ｇ、繊維径１６μｍ、繊維強度２８ｋｇ／
ｍｍ２の活性炭素繊維であった。また、平均細孔径が１
４入、細孔径１０Å以下の容積率が８０％であった。The yield of the obtained activated fibers was 53%, and the specific surface area was 1
480m”/g, fiber diameter 16μm, fiber strength 28kg/
It was activated carbon fiber of mm2. In addition, the average pore diameter is 1
4 pieces, the volume ratio of pores with a diameter of 10 Å or less was 80%.
裏１１犯主
実施例１で得た球状ピッチ繊維を回分式の炉を用いて、
空気中３１０°Ｃまで昇温して不融化を行った後、引続
き雰囲気中に３３％の水蒸気を含む窒素ガスを流通させ
て昇温し、この中で８００°Ｃで４時間保持することに
より賦活化処理を行った。Back 11 Main Example The spherical pitch fiber obtained in Example 1 was processed using a batch furnace.
After making it infusible by raising the temperature to 310°C in air, the temperature was raised by passing nitrogen gas containing 33% water vapor into the atmosphere, and the temperature was kept at 800°C for 4 hours. Activation treatment was performed.
得られた賦活化繊維の収率は４２％であり、比表面積１
７４０ｍ”／ｇ、１６１維径１５μｍ、繊維強度２３ｋ
ｇ／ｍｍ２の活性炭素繊維であった。また、平均細孔径
が１６人、細孔径１０Å以下の容積率が７５％であった
。The yield of the activated fibers obtained was 42%, with a specific surface area of 1
740m”/g, 161 fiber diameter 15μm, fiber strength 23k
g/mm2 activated carbon fiber. Further, the average pore diameter was 16, and the volume percentage with pore diameters of 10 Å or less was 75%.
（発明の効果）
以上説明してきたように、本発明の方法によりコールタ
ールピッチを原料として球状繊維塊活性炭を効率良く製
造することができた。すなわち、本発明の製造方法は、
生産性良く、かつ熱的損失が少ない状態で球状繊維塊活
性炭を製造することができる。しかも、この球状繊維塊
活性炭は、従来の活性炭、すなわち粒状活性炭、粉末状
活性炭、繊維状活性炭に比べて吸着能力が高く、吸着脱
着速度が速く、ハンドリング性および形状維持特性が良
く、再生使用が容易で、機能性の改良がなされている。(Effects of the Invention) As explained above, by the method of the present invention, spherical fiber aggregate activated carbon could be efficiently produced using coal tar pitch as a raw material. That is, the manufacturing method of the present invention
Spherical fiber aggregate activated carbon can be produced with good productivity and with little thermal loss. In addition, this spherical fiber aggregate activated carbon has higher adsorption capacity, faster adsorption/desorption rate, better handling and shape retention characteristics, and is easier to reuse than conventional activated carbon, namely granular activated carbon, powdered activated carbon, and fibrous activated carbon. Easy to use and has improved functionality.
従って、かかる球状繊維塊活性炭は、高吸着脱着能力お
よび広い表面積を活かして、幅広い産業分野で利用され
ている活性炭として極めて優れた特性を有し、公害防止
および環境浄化の他に、食品工業、石油工業等幅広い分
野で用いることができ、高度処理技術に不可欠なものと
して産業上極めて有用である。Therefore, such spherical fiber aggregate activated carbon has extremely excellent properties as an activated carbon that is used in a wide range of industrial fields by taking advantage of its high adsorption and desorption ability and wide surface area. It can be used in a wide range of fields such as the petroleum industry, and is extremely useful industrially as essential for advanced processing technology.
Claims (1)
この紡糸用ピッチを溶融紡糸した後、球状化処理を施し
、次いで酸化性雰囲気で不融化し、さらに賦活化処理す
ることを特徴とする球状繊維塊活性炭の製造方法1. Prepare pitch for spinning using tar pitch as raw material,
A method for producing a spherical fiber mass activated carbon, which comprises melt-spinning this spinning pitch, subjecting it to a spheroidizing treatment, then infusible in an oxidizing atmosphere, and further subjecting it to an activation treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1277157A JPH03146722A (en) | 1989-10-26 | 1989-10-26 | Production of activated carbon composed of spherical fiber lump |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1277157A JPH03146722A (en) | 1989-10-26 | 1989-10-26 | Production of activated carbon composed of spherical fiber lump |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03146722A true JPH03146722A (en) | 1991-06-21 |
Family
ID=17579596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1277157A Pending JPH03146722A (en) | 1989-10-26 | 1989-10-26 | Production of activated carbon composed of spherical fiber lump |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03146722A (en) |
-
1989
- 1989-10-26 JP JP1277157A patent/JPH03146722A/en active Pending
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