JPH0665814A - Precursor of activated carbon fiber and its production - Google Patents
Precursor of activated carbon fiber and its productionInfo
- Publication number
- JPH0665814A JPH0665814A JP4237572A JP23757292A JPH0665814A JP H0665814 A JPH0665814 A JP H0665814A JP 4237572 A JP4237572 A JP 4237572A JP 23757292 A JP23757292 A JP 23757292A JP H0665814 A JPH0665814 A JP H0665814A
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- fiber
- precursor
- pitch
- concentration
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は細孔径の大きい電気二重
層キャパシタや電池などの分極性電極材として有用な活
性炭素繊維製造用前駆体、及び生産性に優れ、高収率で
活性炭素繊維を得ることができる、活性炭素繊維用前駆
体の製造方法に関する。FIELD OF THE INVENTION The present invention relates to a precursor for producing activated carbon fiber which is useful as a polarizable electrode material for electric double layer capacitors and batteries having a large pore size, and an activated carbon fiber which is excellent in productivity and high in yield. And a method for producing a precursor for activated carbon fiber, which is capable of obtaining
【０００２】[0002]
【従来の技術】活性炭素繊維は吸着速度が大きく、しか
も繊維形状のため、一般の粒状もしくは粉末状活性炭に
比べ、粉塵の発生がなく取扱い易く、又種々の形状に加
工することが容易である等の利点を有する。2. Description of the Related Art Activated carbon fibers have a high adsorption rate and are in the form of fibers, so that they are easier to handle and generate various dusts as compared with general granular or powdery activated carbon. And so on.
【０００３】しかしながら、繊維形状とするために、生
産性に劣り高価格となる問題がある。However, because of the fiber shape, there is a problem that the productivity is poor and the cost is high.
【０００４】従来の活性炭素繊維の製造方法としてはレ
ーヨン等の天然繊維、あるいはポリビニルアルコール、
ポリアクリロニトリル、フェーノールノボラック繊維等
の合成繊維を原料とし、不融化後、賦活する製造方法が
行われている。Conventional methods for producing activated carbon fibers include natural fibers such as rayon, polyvinyl alcohol,
A manufacturing method has been performed in which synthetic fibers such as polyacrylonitrile and phenol novolac fibers are used as a raw material, and the synthetic fibers are infusibilized and then activated.
【０００５】これらの原料は高価であり、あるいは不融
化、賦活条件が著しく限定されており、得られる活性炭
素繊維は高価とならざるを得なかった。[0005] These raw materials are expensive, or the infusibilization and activation conditions are extremely limited, and the resulting activated carbon fiber must be expensive.
【０００６】そこで特開平４―１２６８２５号公報に開
示されるように、石油、あるいは石炭等から得られる原
料的に安価なピッチ類を原料に、これを溶融紡糸し、そ
の後、不融化し、賦活することによって、安価な活性炭
素繊維を製造する方法がある。Therefore, as disclosed in Japanese Patent Application Laid-Open No. 4-126825, pitches obtained from petroleum, coal, etc., which are inexpensive as raw materials, are melt-spun, and then infusible and activated. By doing so, there is a method for producing an inexpensive activated carbon fiber.
【０００７】しかしながら原料となるピッチ類が安価な
ものの、不融化工程で長時間を要し生産性が低く得られ
る活性炭素繊維は高価にならざるを得なかった。However, although the pitches used as the raw materials are inexpensive, the activated carbon fibers which require a long time in the infusibilization step and have low productivity have to be expensive.
【０００８】ピッチ類を紡糸し、得られたピッチ繊維を
不融化する際に生産性が低い理由は、通常不融化操作
が、ピッチ繊維が軟化しない低い温度から、空気を用い
て酸化反応を進めるために、不融化の反応が緩慢で、活
性炭素繊維にするに必要な不融化を進めるには長時間を
有するといった問題があった。The reason why the productivity is low when the pitches are spun and the obtained pitch fibers are infusibilized is that the infusibilization operation is usually carried out by using air to promote the oxidation reaction from a low temperature at which the pitch fibers are not softened. Therefore, there has been a problem that the reaction of infusibilization is slow, and it takes a long time to proceed with the infusibilization necessary for forming the activated carbon fiber.
【０００９】ピッチ繊維の不融化反応の促進を行うため
に、特開昭５５―９０６２１では空気に二酸化窒素を混
入することによって１段で不融化反応を行い、不融化で
の反応を促進させ生産性を向上させる炭素繊維の製造方
法が示されている。In order to accelerate the infusibilizing reaction of pitch fibers, in JP-A-55-90621, by mixing nitrogen dioxide into air, the infusibilizing reaction is carried out in a single stage to promote the reaction in infusibilizing. A method for producing a carbon fiber that improves the properties is shown.
【００１０】不融化時に二酸化窒素を用いることによ
り、低温度での反応性が向上し、不融化時間の短縮が可
能となる。しかしながら、この方法では賦活時の収率が
著しく低下するといった問題が生じた。By using nitrogen dioxide at the time of infusibilization, the reactivity at low temperature is improved and the infusibilization time can be shortened. However, this method has a problem that the yield upon activation is significantly reduced.
【００１１】[0011]
【発明が解決しようとする課題】本発明は、安価である
ピッチ繊維を原料とし、二酸化窒素を用いて不融化を促
進させ、且つ賦活収率が高い、活性炭素繊維用前駆体の
製造方法を提供することにある。DISCLOSURE OF THE INVENTION The present invention provides a method for producing a precursor for activated carbon fiber, which is prepared from inexpensive pitch fiber as a raw material, promotes infusibilization by using nitrogen dioxide, and has a high activation yield. To provide.
【００１２】[0012]
【課題を解決するための手段】本発明は、 （１）等方性ピッチを紡糸して得られたピッチ繊維を、
二酸化窒素（ＮＯ 2）と酸素（Ｏ2）を含む酸化性ガス雰
囲気中で、連続又は多段でＮＯ2濃度を次第に低めなが
ら不融化処理することにより得られた活性炭素繊維用前
駆体の製造方法、The present invention provides (1) a pitch fiber obtained by spinning an isotropic pitch,
Nitrogen dioxide (NO 2) And oxygen (O2) Containing an oxidizing gas atmosphere
NO in continuous or multiple stages in the atmosphere2The concentration gradually decreases
Before activated carbon fiber obtained by infusibilizing treatment from
Manufacturing method
【００１３】（２）不融化処理を２段で行い、１段目の
不融化処理を二酸化窒素濃度が５〜１０体積％、酸素濃
度が５〜３０体積％、残部が主として不活性ガスからな
る酸化性ガス雰囲気下、温度１００〜２５０℃で１時間
以上行い、次いで２段目の不融化処理を二酸化窒素濃度
が０．１〜５体積％、酸素濃度が５〜４０体積％、残部
が主として不活性ガスからなる酸化性ガス雰囲気下、温
度２００〜３５０℃で１時間以上行うことを特徴とする
（１）記載の方法、(2) The infusibilizing treatment is carried out in two steps, and the infusibilizing treatment in the first step is made to have a nitrogen dioxide concentration of 5 to 10% by volume, an oxygen concentration of 5 to 30% by volume, and the balance mainly consisting of an inert gas. It is carried out in an oxidizing gas atmosphere at a temperature of 100 to 250 ° C. for 1 hour or more, and then the second step of infusibilizing treatment is carried out with a nitrogen dioxide concentration of 0.1 to 5% by volume, an oxygen concentration of 5 to 40% by volume, and the balance mainly. The method according to (1), which is carried out at a temperature of 200 to 350 ° C. for 1 hour or more in an oxidizing gas atmosphere containing an inert gas.
【００１４】（３）残部が不活性ガスの他５〜１０体積
％の水蒸気を含有するものである（２）記載の方法、(3) The method according to (2), wherein the balance contains 5 to 10% by volume of water vapor in addition to the inert gas.
【００１５】（４）請求項１記載の方法によって得られ
た不融化繊維のＯ／Ｃの原子数比が０．０５〜０．１０
であり、且つＯ／Ｎの原子数比が４．５以上である活性
炭素繊維前駆体、(4) The infusible fiber obtained by the method according to claim 1 has an O / C atomic ratio of 0.05 to 0.10.
And an activated carbon fiber precursor having an O / N atomic ratio of 4.5 or more,
【００１６】（５）等方性ピッチを紡糸して得られたピ
ッチ繊維を、二酸化窒素（ＮＯ 2）と酸素（Ｏ2）を含む
酸化性ガス雰囲気中で、連続又は多段でＮＯ2濃度を次
第に低めながら不融化処理し、次いで温度３００〜６０
０℃で、不活性ガス雰囲気で炭化処理することを特徴と
する活性炭素繊維用前駆体の製造方法、である。(5) A pigment obtained by spinning an isotropic pitch.
Fiber, nitrogen dioxide (NO 2) And oxygen (O2)including
NO continuously or in multiple stages in an oxidizing gas atmosphere2Next concentration
First, infusibilizing treatment while lowering, then temperature 300 to 60
Characterized by carbonization at 0 ° C. in an inert gas atmosphere
A method for producing a precursor for activated carbon fibers, which comprises:
【００１７】以下、本発明の内容を詳細に説明する。The details of the present invention will be described below.
【００１８】本発明の活性炭素繊維前駆体の出発原料で
あるピッチは、コールタール、コールタールピッチ等の
石炭系ピッチ、石炭液化ピッチ、エチレンタールピッ
チ、流動接触、石油分解残渣油から得られるデカントオ
イルピッチ等の石油系ピッチ、あるいはナフタレン等か
ら触媒などを用いて作られる合成ピッチ等、各種のピッ
チを包含するものである。The starting material of the activated carbon fiber precursor of the present invention is a pitch derived from coal-based pitch such as coal tar and coal tar pitch, coal liquefied pitch, ethylene tar pitch, fluidized contact, and petroleum cracked residual oil. It includes various pitches such as petroleum pitches such as oil pitches, or synthetic pitches produced from naphthalene or the like using a catalyst or the like.
【００１９】本発明に使用されるピッチは一般に活性炭
素繊維の製造に用いられる等方性ピッチで、好ましく軟
化点が１５０〜３５０℃、より好ましくは２００〜２７
０℃のものがよい。The pitch used in the present invention is an isotropic pitch generally used in the production of activated carbon fibers, preferably having a softening point of 150 to 350 ° C., more preferably 200 to 27.
0 ° C is preferable.
【００２０】この等方性ピッチをたとえばこれまで知ら
れている方法にて溶融紡糸を行うことによりピッチ繊維
が得られる。The isotropic pitch is melt-spun by, for example, a conventionally known method to obtain pitch fibers.
【００２１】例えば、前記ピッチを粘度１００ポイズ〜
２０００ポイズを示す温度で、口径０．１ｍｍ〜０．５
ｍｍのキャピラリーから、圧力０．１〜１００ｋｇ／ｃ
ｍ2程度で押し出しながら１００〜２０００ｍ／ｍｉｎ
の引き取り速度で延伸し、繊維径が５〜２０μｍのピッ
チ繊維を得る。For example, the pitch may have a viscosity of 100 poises.
A caliber of 0.1 mm to 0.5 at a temperature of 2000 poise
mm capillary, pressure 0.1-100kg / c
100 to 2000 m / min while extruding at about m 2
At a take-up speed to obtain pitch fibers having a fiber diameter of 5 to 20 μm.
【００２２】本発明の前駆体繊維は本発明の不融化条件
で処理することによって初めて得られるものである。The precursor fiber of the present invention can be obtained only by treating it under the infusibilizing condition of the present invention.
【００２３】すなわち、本発明では、軟化点が低温部で
は、二酸化窒素濃度を高くし酸化を促進し、軟化点が高
温になるに従い、二酸化窒素濃度を低くして不融化を行
う。ＮＯ2濃度を低くしないと、繊維中のＮが増加し、
賦活収率が低下する。That is, in the present invention, in the low temperature portion where the softening point is low, the concentration of nitrogen dioxide is increased to promote the oxidation, and as the softening point becomes higher, the concentration of nitrogen dioxide is decreased to achieve infusibilization. If the NO 2 concentration is not lowered, N in the fiber will increase,
The activation yield decreases.
【００２４】この方法で賦活収率に優れる不融化前駆体
繊維の得られることを見出し本発明を完成するに至った
ものである。The present invention has been completed by finding that an infusible precursor fiber excellent in activation yield can be obtained by this method.
【００２５】温度を連続的に低温から高温にし、それに
伴い、連続的に二酸化窒素の濃度を高濃度から低濃度に
してもよいが、生産性の上からは、２〜３段の多段に分
けて行うことが現実的である。The temperature may be continuously changed from a low temperature to a high temperature, and accordingly, the concentration of nitrogen dioxide may be continuously changed from a high concentration to a low concentration, but from the viewpoint of productivity, it is divided into two or three stages. It is realistic to do so.
【００２６】具体的に２段の例で説明すると、二酸化窒
素濃度が５〜１０体積％、酸素濃度が５〜３０体積％、
残りのガスを窒素等の不活性ガス、あるいは不活性ガス
と水蒸気とした混合ガス雰囲気下で軟化点より少し低目
の温度１００〜２５０℃で一段目の不融化を行い、次に
二酸化窒素濃度０．１〜５体積％、好ましくは０．２〜
２体積％、酸素濃度が５〜４０体積％、好ましくは１０
〜３０体積％、残りのガスを窒素等の不活性ガス、ある
いは不活性ガスと水蒸気とした混合ガス雰囲気で軟化点
が向上したため、少し高目の温度２００〜３５０℃で二
段目の不融化を行うことによってはじめて、賦活収率に
優れる活性炭素繊維前駆体繊維が得られる。Explaining concretely in a two-stage example, the nitrogen dioxide concentration is 5 to 10% by volume, the oxygen concentration is 5 to 30% by volume,
The remaining gas is an inert gas such as nitrogen, or a mixed gas atmosphere in which an inert gas and water vapor are used, and the first step of infusibilization is performed at a temperature slightly lower than the softening point of 100 to 250 ° C., and then the nitrogen dioxide concentration. 0.1-5% by volume, preferably 0.2-
2% by volume, oxygen concentration 5 to 40% by volume, preferably 10
-30% by volume, the softening point improved in an inert gas such as nitrogen, or a mixed gas atmosphere of an inert gas and water vapor, so the second stage infusible at a slightly higher temperature of 200 to 350 ° C. The activated carbon fiber precursor fiber having an excellent activation yield can be obtained for the first time by carrying out.
【００２７】なお、混合ガス雰囲気中に水蒸気を５〜１
０体積％存在させることによって、若干反応性が向上す
る。多すぎると賦活収率が低下する。It should be noted that 5 to 1 of steam is added to the mixed gas atmosphere.
The presence of 0% by volume slightly improves the reactivity. If it is too large, the activation yield will decrease.
【００２８】また、この不融化糸を必要に応じて炭化す
ることによって、前駆体繊維の強度を向上させ、その後
の賦活操作を容易にすることによっても本発明の前駆体
繊維が得られる。The precursor fiber of the present invention can also be obtained by carbonizing the infusible yarn as required to improve the strength of the precursor fiber and facilitate the subsequent activation operation.
【００２９】本発明の前駆体繊維は、不融化終了後の不
融化繊維の炭素酸素原子数比Ｏ／Ｃが０．０５〜０．１
０、好ましくは０．０６〜０．０９であり、かつ酸素窒
素原子数比Ｏ／Ｎが４．５以上であることが肝要であ
る。この値になるように不融化を進める。The precursor fiber of the present invention has a carbon-oxygen atom number ratio O / C of the infusible fiber after completion of infusibility of 0.05 to 0.1.
It is important that the ratio is 0, preferably 0.06 to 0.09, and the oxygen / nitrogen atom number ratio O / N is 4.5 or more. Infusibilization is advanced to reach this value.
【００３０】Ｏ／Ｃの値が０．０５未満では不融化が不
足であり、賦活時の収率が著しく低下する。When the value of O / C is less than 0.05, the infusibilization is insufficient and the yield upon activation is significantly reduced.
【００３１】同様にＯ／Ｎの値が４．５未満では原因は
定かではないが賦活時の収率が著しく低下する。Similarly, if the O / N value is less than 4.5, the cause is not clear, but the yield at the time of activation is remarkably reduced.
【００３２】Ｏ／Ｃの値が０．１０を超えると不融化時
に導入された酸素が過剰となり、賦活収率の低下、活性
炭素繊維強度の低下を引き起こす。If the value of O / C exceeds 0.10, the oxygen introduced at the time of infusibilization becomes excessive, resulting in a decrease in activation yield and a decrease in activated carbon fiber strength.
【００３３】本発明の前駆体繊維は、水蒸気、二酸化炭
素を含むガス中において温度７５０〜１２００℃の温度
で賦活することによって、高収率で大比表面積の活性炭
素繊維を得ることができる。By activating the precursor fiber of the present invention in a gas containing water vapor and carbon dioxide at a temperature of 750 to 1200 ° C., an activated carbon fiber having a high specific surface area and a high yield can be obtained.
【００３４】また、得られる活性炭素繊維の平均細孔径
が、ピッチから従来方法で得られるものに比べ、本発明
の前駆体繊維から得られる活性炭素繊維は第１表で示す
ように平均細孔径が大きく、電気二重層キャパシタや電
池などの分極性電極材として特に有用である。Further, the average pore size of the obtained activated carbon fibers is larger than that obtained by the conventional method from the pitch, the activated carbon fibers obtained from the precursor fibers of the present invention have an average pore size as shown in Table 1. It is particularly useful as a polarizable electrode material for electric double layer capacitors and batteries.
【００３５】本発明の不融化繊維を、温度３００〜６０
０℃、より好ましくは３７０〜４５０℃で、窒素ガス等
の不活性ガス雰囲気で炭化処理することにより、不融化
糸よりさらに繊維の強度を改善し、活性炭素繊維用前駆
体繊維とすることもできる。The infusible fiber of the present invention is treated at a temperature of 300 to 60.
It is also possible to further improve the strength of the fiber as compared with the infusibilized yarn by carbonizing at 0 ° C., more preferably 370 to 450 ° C. in an inert gas atmosphere such as nitrogen gas to obtain a precursor fiber for activated carbon fiber. it can.
【００３６】[0036]
【作用】一般に、ピッチ類から活性炭を製造する場合に
は、不融化（酸化）を充分に行うことによって細孔の形
成が容易になるといわれている。In general, it is said that in the case of producing activated carbon from pitches, the formation of pores is facilitated by sufficient infusibilization (oxidation).
【００３７】酸化ガスとして二酸化窒素を用いると、酸
化反応の進行が進むものの、繊維内部と外側での反応に
不均質が生じ、内部は酸化が不足し、外側が過剰に酸化
することとなる。When nitrogen dioxide is used as the oxidizing gas, the progress of the oxidation reaction proceeds, but the reaction inside and outside the fiber becomes inhomogeneous, the inside is insufficiently oxidized, and the outside is excessively oxidized.
【００３８】一方、空気のように酸化反応性の低いガス
の場合、均質な酸化が行われるものの、酸化に要する時
間が長時間を要する。On the other hand, in the case of a gas having a low oxidation reactivity such as air, a uniform oxidation is carried out, but a long time is required for the oxidation.
【００３９】また、原因は明かではないが、二酸化窒素
による酸化を行うことにより、過剰に窒素元素が繊維に
取り込まれると、賦活時の収率が著しく低下するのであ
る。Although the cause is not clear, if the nitrogen element is excessively taken into the fiber by performing the oxidation with nitrogen dioxide, the yield at the time of activation is remarkably reduced.
【００４０】本発明の前駆体繊維では、たとえば２段階
の酸化条件を設けることにより、酸化反応性を低下させ
ることなく均質に酸化されており、しかも窒素原子の取
り込みが少ないために賦活収率が高いものと思われる。In the precursor fiber of the present invention, by providing, for example, two-step oxidation conditions, the precursor fiber is uniformly oxidized without lowering the oxidation reactivity, and the incorporation yield of nitrogen atoms is small, so that the activation yield is high. Seems expensive.
【００４１】[0041]
【実施例】以下、さらに本発明を、実施例ならびに比較
例を用いて具体的に説明する。なお、本発明において、
ピッチ系炭素繊維および原料ピッチの特性を表わすのに
用いた諸物性値は以下の定義によった。EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples. In the present invention,
The physical property values used to express the characteristics of the pitch-based carbon fiber and the raw material pitch are defined as follows.
【００４２】（１）軟化点 軟化点は、フローテスターを用いてハーゲン・ポアズイ
ユ式から算出される見掛けの粘度が２００００ポイズと
なる温度である。(1) Softening Point The softening point is the temperature at which the apparent viscosity calculated from the Hagen-Poiseuille equation using a flow tester becomes 20000 poise.
【００４３】（２）トルエン不溶分、キノリン不溶分 トルエン不溶分、キノリン不溶分はＪＩＳ―Ｋ―２４２
５（１９７８年）に示された方法に準じて測定した。(2) Toluene-insoluble matter and quinoline-insoluble matter Toluene-insoluble matter and quinoline-insoluble matter are JIS-K-242.
5 (1978).
【００４４】 （３）元素分析によるＯ／Ｃ、Ｏ／Ｎ原子数比 繊維を長さ１ｍｍ程度に切断した後、窒素中１００℃で
１ｈｒ乾燥した後、デシケータ中で徐冷したサンプル
を、炭素、水素、窒素についてはＣＨＮコーダーを用い
て、酸素については酸素微量定量分析装置で各元素の重
量分率を求め、これにより原子数比を求めた。(3) O / C and O / N atomic number ratio by elemental analysis The fiber was cut into a length of about 1 mm, dried in nitrogen at 100 ° C. for 1 hr, and then slowly cooled in a desiccator. For hydrogen and nitrogen, a CHN coder was used, and for oxygen, the weight fraction of each element was determined by an oxygen trace quantitative analyzer, and the atomic ratio was determined.
【００４５】[0045]
【実施例、比較例】原料としてキノリン不溶分を除去し
た軟化点８０℃のコールタールピッチを常圧下４５０℃
で熱処理した後、低沸点分を除き紡糸用ピッチを得た。Examples and Comparative Examples Coal tar pitch having a softening point of 80 ° C. from which quinoline insoluble matter has been removed is used as a raw material at 450 ° C. under normal pressure.
After heat treatment in, a low boiling point component was removed to obtain a spinning pitch.
【００４６】このピッチは、軟化点が２５０℃、トルエ
ン不溶分が６０重量％、キノリン不溶分が痕跡量であ
り、メソフェースを全く含まない光学的等方性ピッチで
あった。The pitch was an optically isotropic pitch having a softening point of 250 ° C., a toluene insoluble content of 60% by weight, a quinoline insoluble content of a trace amount, and no mesophase.
【００４７】このピッチを用いて、内径０．２ｍｍのキ
ャピラリーを３０００ホール有する口金を用いて、紡糸
を行い繊維径１５μｍ、フィラメント数３０００のピッ
チ繊維を得た。Using this pitch, a spinneret having 3000 holes of 0.2 mm inner diameter capillary was spun to obtain a pitch fiber having a fiber diameter of 15 μm and a filament number of 3000.
【００４８】このピッチ繊維は炭素が９４．１重量％、
水素が４．２重量％、窒素が０．８重量％、酸素が０．
９重量％であった。This pitch fiber contains 94.1% by weight of carbon,
Hydrogen is 4.2% by weight, nitrogen is 0.8% by weight, and oxygen is 0.
It was 9% by weight.
【００４９】このピッチ繊維を第１表に示すガス雰囲気
条件で、前段１２０〜２４０℃の温度で１時間、後段２
４０〜３２０℃の温度で１時間、計２時間で処理した。This pitch fiber was subjected to gas atmosphere conditions shown in Table 1 for 1 hour at a temperature of 120 to 240 ° C. in the first stage, and 2 in the second stage.
The treatment was carried out at a temperature of 40 to 320 ° C. for 1 hour, for a total of 2 hours.
【００５０】得られた前駆体繊維（不融化糸）をＬＰＧ
燃焼ガス中、約１０００℃の温度で賦活処理を行った。
得られた活性炭素繊維の液体窒素温度における窒素吸着
量からＢＥＴ比表面積が１５００ｍ2／ｇになるように
賦活時間を定めた。The obtained precursor fiber (infusibilized yarn) was LPG.
The activation treatment was performed in a combustion gas at a temperature of about 1000 ° C.
The activation time was determined so that the BET specific surface area would be 1500 m 2 / g based on the nitrogen adsorption amount of the obtained activated carbon fiber at the liquid nitrogen temperature.
【００５１】得られた活性炭素繊維の重量と、供した前
駆体繊維の重量から賦活歩留まりを算出した。また、得
られた活性炭素繊維は液体窒素温度における窒素吸着量
から細孔径を求めた。第１表に結果を掲げた。The activation yield was calculated from the weight of the obtained activated carbon fiber and the weight of the precursor fiber provided. The pore size of the obtained activated carbon fiber was determined from the amount of nitrogen adsorbed at the liquid nitrogen temperature. The results are listed in Table 1.
【００５２】実験Ｎｏ．１〜３は比較例で雰囲気条件が
本発明範囲外であるため原子数比が本発明範囲外とな
り、賦活収率（歩留り）が良くなかった。Experiment No. In Comparative Examples 1 to 3, the atmospheric conditions were outside the range of the present invention, so the atomic ratio was outside the range of the present invention, and the activation yield (yield) was poor.
【００５３】Ｎｏ．８は空気雰囲気の場合で前段、後段
２時間の熱処理では不融化せず、繊維が融着した。No. In No. 8 in the case of an air atmosphere, the fibers were fused without being infusibilized by the heat treatment of the former stage and the latter stage for 2 hours.
【００５４】Ｎｏ．９は酸素量を増した場合で繊維が不
融化中に燃焼した。No. No. 9 was a case where the amount of oxygen was increased, and the fiber burned during infusibilization.
【００５５】Ｎｏ．１０は１００〜３２０℃、７時間で
不融化したところ、細孔径の小のものが得られた。No. No. 10 was infusibilized at 100 to 320 ° C. for 7 hours, and a small pore size was obtained.
【００５６】Ｎｏ．４〜７は本発明実施例で良好な歩留
りと細孔径を得た。No. In Nos. 4 to 7, good yield and fine pore size were obtained in Examples of the present invention.
【００５７】Ｎｏ．１１、１３はＮＯ2濃度を変えない
１段不融化の例であり、Ｎｏ．１２は２段において前段
のみにＮＯ2を含有する例であるが、いずれもＯ／Ｃ及
び／又はＯ／Ｎの値が範囲外となり、歩留りが悪い。No. Nos. 11 and 13 are examples of one-step infusibilization that does not change the NO 2 concentration. No. 12 is an example in which NO 2 is contained only in the preceding stage in the second stage, but in both cases, the values of O / C and / or O / N are out of the range, and the yield is poor.
【００５８】[0058]
【表１】 [Table 1]
【００５９】[0059]
【表２】 [Table 2]
【００６０】[0060]
【発明の効果】本発明により、安価なピッチ繊維を原料
として、生産性、賦活収率の高い、活性炭素繊維用前駆
体が得られる。Industrial Applicability According to the present invention, a precursor for activated carbon fiber having high productivity and high activation yield can be obtained from inexpensive pitch fiber as a raw material.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 荒井 豊 川崎市中原区井田1618番地 新日本製鐵株 式会社先端技術研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yutaka Arai 1618 Ida, Nakahara-ku, Kawasaki City Nippon Steel Corp. Advanced Technology Research Laboratories
Claims (5)
繊維を、二酸化窒素（ＮＯ 2）と酸素（Ｏ2）を含む酸化
性ガス雰囲気中で、連続又は多段でＮＯ2濃度を次第に
低めながら不融化処理することにより得られた活性炭素
繊維用前駆体の製造方法。1. A pitch obtained by spinning an isotropic pitch.
The fiber is replaced with nitrogen dioxide (NO 2) And oxygen (O2) Containing oxidation
NO in continuous or multi-stage in a volatile gas atmosphere2Concentration gradually
Activated carbon obtained by infusibilizing treatment while lowering
A method for producing a precursor for fibers.
化処理を二酸化窒素濃度が５〜１０体積％、酸素濃度が
５〜３０体積％、残部が主として不活性ガスからなる酸
化性ガス雰囲気下、温度１００〜２５０℃で１時間以上
行い、次いで２段目の不融化処理を二酸化窒素濃度が
０．１〜５体積％、酸素濃度が５〜４０体積％、残部が
主として不活性ガスからなる酸化性ガス雰囲気下、温度
２００〜３５０℃で１時間以上行うことを特徴とする請
求項１記載の方法。2. The infusibilizing treatment is carried out in two stages, and the infusibilizing treatment in the first stage is an oxidation in which the nitrogen dioxide concentration is 5 to 10% by volume, the oxygen concentration is 5 to 30% by volume, and the balance is mainly an inert gas. It is performed for 1 hour or more at a temperature of 100 to 250 ° C. under an inert gas atmosphere, and then the second step of infusibilizing treatment is carried out with a nitrogen dioxide concentration of 0.1 to 5% by volume, an oxygen concentration of 5 to 40% by volume, and the balance being mainly insoluble. The method according to claim 1, wherein the method is carried out at a temperature of 200 to 350 ° C. for 1 hour or more in an oxidizing gas atmosphere containing an active gas.
水蒸気を含有するものである請求項２記載の方法。3. The method according to claim 2, wherein the balance contains 5 to 10% by volume of water vapor in addition to the inert gas.
融化繊維のＯ／Ｃの原子数比が０．０５〜０．１０であ
り、且つＯ／Ｎの原子数比が４．５以上である活性炭素
繊維前駆体。4. The infusible fiber obtained by the method according to claim 1 has an O / C atomic ratio of 0.05 to 0.10 and an O / N atomic ratio of 4.5 or more. Is an activated carbon fiber precursor.
繊維を、二酸化窒素（ＮＯ 2）と酸素（Ｏ2）を含む酸化
性ガス雰囲気中で、連続又は多段でＮＯ2濃度を次第に
低めながら不融化処理し、次いで温度３００〜６００℃
で、不活性ガス雰囲気で炭化処理することを特徴とする
活性炭素繊維用前駆体の製造方法。5. A pitch obtained by spinning an isotropic pitch.
The fiber is replaced with nitrogen dioxide (NO 2) And oxygen (O2) Containing oxidation
NO in continuous or multi-stage in a volatile gas atmosphere2Concentration gradually
Infusibilizing treatment while lowering, then temperature 300-600 ℃
It is characterized by being carbonized in an inert gas atmosphere
A method for producing a precursor for activated carbon fiber.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4237572A JP3071315B2 (en) | 1992-08-14 | 1992-08-14 | Precursor for activated carbon fiber and production method |
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| KR20180087196A (en) * | 2017-01-24 | 2018-08-01 | 전남대학교산학협력단 | High electric conductive carbon fiber and method of manufacturing the same |
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