JPH0356599B2 - - Google Patents
Info
- Publication number
- JPH0356599B2 JPH0356599B2 JP2612784A JP2612784A JPH0356599B2 JP H0356599 B2 JPH0356599 B2 JP H0356599B2 JP 2612784 A JP2612784 A JP 2612784A JP 2612784 A JP2612784 A JP 2612784A JP H0356599 B2 JPH0356599 B2 JP H0356599B2
- Authority
- JP
- Japan
- Prior art keywords
- pitch
- solvent
- carbon
- carbon fiber
- treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000011295 pitch Substances 0.000 claims description 44
- 239000002243 precursor Substances 0.000 claims description 20
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 18
- 239000004917 carbon fiber Substances 0.000 claims description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000011271 tar pitch Substances 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 230000005587 bubbling Effects 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 238000003763 carbonization Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011338 soft pitch Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Working-Up Tar And Pitch (AREA)
- Inorganic Fibers (AREA)
Description
【発明の詳細な説明】
技術分野
炭素繊維プリカーサーピツチの製造方法に関し
て、この明細書で述べる技術内容は、とくに原料
タールピツチからの溶剤抽出処理に工夫を加える
ことにより、上記プリカーサーピツチの熱安定
性、紡糸性および不融化性、さらには炭化収率な
どを改善することに関連している。[Detailed Description of the Invention] Technical Field Regarding the method for producing carbon fiber precursor pitch, the technical contents described in this specification are particularly focused on improving the thermal stability of the precursor pitch by adding a device to the solvent extraction process from the raw material tar pitch. It is related to improving spinnability, infusibility, and carbonization yield.
従来技術とその問題点
炭素繊維の製造法は、ポリアクリロニトリルな
どの合成繊維を原料とする方法と、石油ピツチ、
タールピツチを原料とする方法とに大別される。Conventional technology and its problems There are two methods for producing carbon fiber: one using synthetic fibers such as polyacrylonitrile, and the other using petroleum pitch,
There are two main types of methods: methods that use tar pithu as raw material.
ところで上掲した二つの方法のうち、前述の方
法には、原料の繊維が高価であることのほか原料
繊維の炭化比率が低いという欠点があつた。また
後者の場合は、一般に原料ピツチが紡糸性の良い
ものは不融化性に劣り、一方不融化性の良いもの
は紡糸性に劣るという相反する性質をそなえてい
て、両性質を兼備させることは難しいという欠点
があつた。さらに後者の方法によつて炭素繊維を
製造する場合は、原料ピツチから炭素繊維の前駆
体としてのプリカーサーピツチを調整することが
不可欠であるが、かかるプリカーサーピツチの調
製に当つては、原料ピツチ中に分散する微小な不
溶性固形分（フリーカーボンや無機質）の除去が
難しいことのほかに、水素ガスによる高圧下での
水素化または特殊な水素供与性溶剤による水素化
による紡糸性ならびに不融化性の改善処理を必要
とするところにも問題を残していた。 By the way, among the two methods mentioned above, the above-mentioned method has the disadvantage that the raw material fiber is expensive and the carbonization ratio of the raw material fiber is low. In the latter case, raw material pitches that have good spinnability are generally inferior in infusibility, while those with good infusibility are poor in spinnability, and it is difficult to combine both properties. It had the drawback of being difficult. Furthermore, when producing carbon fibers by the latter method, it is essential to prepare a precursor pitch as a precursor of carbon fiber from the raw material pitch. In addition to the difficulty in removing minute insoluble solids (free carbon and inorganic substances) dispersed in the water, it is difficult to remove spinnability and infusibility by hydrogenation under high pressure with hydrogen gas or hydrogenation with a special hydrogen-donating solvent. Problems remained in areas that required improvement.
発明の目的
この発明は、上述した如き諸問題を有利に解決
するもので、水素化処理などの特殊な処理を行う
必要なしに、熱安定性、紡糸性および不融化性に
優れ、また炭化収率が高く、さらにフリーカーボ
ンや灰分などの不溶性固形分を含まず、しかも炭
素繊維とした場合に充分な強度および弾性率をそ
なえてなる炭素繊維プリカーサーピツチの製造方
法を提供することを目的とする。Purpose of the Invention The present invention advantageously solves the above-mentioned problems, and has excellent thermal stability, spinnability, and infusibility without the need for special treatment such as hydrogenation treatment, and has excellent carbonization absorption. The purpose of the present invention is to provide a method for producing a carbon fiber precursor pitch which has a high carbon fiber precursor pitch, does not contain insoluble solids such as free carbon and ash, and has sufficient strength and elastic modulus when made into carbon fibers. .
発明の端緒
この発明は、タールピツチの溶剤抽出を高温、
高圧の状態すなわち臨界状態で行うようにすれ
ば、溶剤の密度が低下して溶剤不溶成分の沈降速
度が著しく増加し、該不溶成分の分離除去が極め
て容易に実現することの新規知見に立脚する。Origin of the invention This invention involves the solvent extraction of tarpitz at high temperature.
Based on the new knowledge that if the process is carried out under high pressure, that is, in a critical state, the density of the solvent decreases and the sedimentation rate of solvent-insoluble components increases significantly, making it extremely easy to separate and remove these insoluble components. .
発明の構成
すなわちこの発明は、タールピツチに、芳香族
系沸点溶剤による臨界状態での抽出処理を施して
溶剤不溶分を分離除去したのち、抽出液からさら
に溶剤を除去してフリーカーボンを含まないピツ
チとし、ついで得られたピツチに加熱処理を施す
ことから成る炭素繊維プリカーサーピツチの製造
方法である。Structure of the Invention In other words, the present invention subjects tar pitch to extraction treatment in a critical state with an aromatic boiling point solvent to separate and remove solvent-insoluble components, and then further removes the solvent from the extract to produce pitch that does not contain free carbon. This is a method for producing a carbon fiber precursor pitch, which comprises preparing a carbon fiber precursor pitch and then subjecting the obtained pitch to a heat treatment.
この発明に従い、臨界状態で溶剤抽出を行うこ
とすなわち、フリーカーボンを含むタールピツチ
を１〜５倍容量好ましくは２〜2.5倍容量の芳香
族系低沸点溶剤たとえばガス軽油に溶解してから
260〜320℃に加熱し、30〜60気圧での加圧処理を
施すことによつて、該ピツチ中のフリーカーボン
を効果的に除去することができ、ひいては水素化
処理などの特別な処理を施すことなしに、熱安定
性が良く、また紡糸性および不融化性に優れ、し
かも炭化収率が高い炭素繊維用のプリカーサーピ
ツチを容易に製造することができるようになつた
のである。 According to the invention, solvent extraction is carried out in a critical state, i.e. after dissolving the tar pitch containing free carbon in 1 to 5 times the volume, preferably 2 to 2.5 times the volume of an aromatic low-boiling solvent such as gas light oil.
Free carbon in the pit can be effectively removed by heating it to 260-320℃ and pressurizing it at 30-60 atm. It has now become possible to easily produce a precursor pitch for carbon fibers that has good thermal stability, excellent spinnability and infusibility, and has a high carbonization yield without the need for carbonization.
なおこの発明において、抽出処理後、不溶成分
を分離除去したピツチに施す加熱処理は、減圧下
または不活性ガスのバブリング下における350〜
450℃の温度範囲での熱処理することがより好ま
しい。 In this invention, after the extraction process, the heat treatment applied to the pitch from which insoluble components have been separated and removed is carried out at a temperature of 350 to
More preferably, the heat treatment is carried out in a temperature range of 450°C.
以下この発明を具体的に説明する。 This invention will be explained in detail below.
さてピツチ類には通常、直径1μｍ以下の微粒
子であるフリーカーボンおよび灰分となる無機質
などが不溶性固型分として含まれているが、かよ
うなピツチを炭素繊維の原料ピツチとして用いる
場合には、上記した如き不溶性固型分を除去して
おく必要がある。というのは、ピツチ中にかかる
不純物が存在すると溶融紡糸が困難となり、また
炭素繊維のボイドの発生や強度の低下を招く原因
ともなるからである。 Now, pitches usually contain free carbon, which is fine particles with a diameter of 1 μm or less, and inorganic substances, which become ash, as insoluble solids, but when such pitches are used as raw material pitch for carbon fiber, It is necessary to remove insoluble solids as described above. This is because the presence of such impurities in the pitch makes melt spinning difficult and also causes voids to occur in the carbon fibers and a decrease in strength.
この点、この発明に従う臨界状態での抽出処理
によれば、フリーカーボンや灰分はいうまでもな
く、ピツチ中に存在する高分子量成分も溶剤不溶
成分として同時に分離除去されるため、炭素繊維
用原料としてより一層優れた特性が与えられるこ
とになるのである。つまり上述のようにして溶剤
不溶分を除去したピツチは、従来のものに較べて
熱安定性の著しい改善がみられたのである。 In this regard, according to the extraction process in a critical state according to the present invention, not only free carbon and ash but also high molecular weight components present in the pitch are simultaneously separated and removed as solvent-insoluble components. As a result, even more excellent properties will be provided. In other words, the pitch from which the solvent-insoluble matter was removed as described above showed a marked improvement in thermal stability compared to the conventional pitch.
その後抽出液から溶剤を除去してフリーカーボ
ンを含まないピツチとしたのち、このピツチに加
熱処理を施して該ピツチ中の低分子量成分を除去
するととともに、ピツチの高分子化を図ることに
より、炭素繊維プリカーサーピツチとするわけで
ある。 After that, the solvent is removed from the extract to make a pitch that does not contain free carbon, and this pitch is then heat-treated to remove low molecular weight components in the pitch and to make the pitch into a polymer. This is called a fiber precursor pitch.
かようなプリカーサーピツチの調製工程におい
て、ピツチ中の低分子量成分を有効に除去するた
めには、該ピツチの加熱処理を、350〜450℃の温
度範囲にて、減圧下またはArやN2ガスの如き不
活性ガスのバブリング下に行うことがより好まし
く、また得られたプリカーサーピツチの特性は、
軟化点：200℃以上でかつ、ベンゼン不溶分：45
〜65重量％（以下単に％で示す）、キノリン不溶
分：0.5％以下であることが望ましい。というの
はかかる条件を満足するプリカーサーピツチは、
溶融紡糸性および不融化性がとりわけ良好となる
からである。 In the precursor pitch preparation process, in order to effectively remove low molecular weight components in the pitch, the pitch must be heated at a temperature range of 350 to 450°C under reduced pressure or using Ar or N 2 gas. It is more preferable to conduct the process under bubbling of an inert gas such as, and the characteristics of the obtained precursor pitch are as follows.
Softening point: 200℃ or higher and benzene insoluble content: 45
~65% by weight (hereinafter simply expressed as %), quinoline insoluble content: preferably 0.5% or less. This is because the precursor pitch that satisfies these conditions is
This is because melt spinnability and infusibility become particularly good.
なお上記した加熱処理においては、できる限り
メソフエーズの発生が抑制されるように、処理条
件を設定しなければならないが、この発明に従う
ピツチは熱的安定性が極めて優れており、従つて
処理条件をことさら厳しくする必要はなく、350
〜450℃程度の加熱処理により、メソフエーズの
生成を充分に抑制しつつ、ベンゼン不溶分：45〜
65％の炭素繊維プリカーサーピツチを製造するこ
とができる。 In the heat treatment described above, the treatment conditions must be set so that the generation of mesophase is suppressed as much as possible, but the pitch according to the present invention has extremely excellent thermal stability, so the treatment conditions must be There is no need to be particularly strict; 350
Heat treatment at ~450°C sufficiently suppresses the formation of mesophase while reducing benzene insoluble content: 45 ~
65% carbon fiber precursor pitch can be produced.
かくして得られたプリカーサーピツチは、通常
の溶融紡糸性によつて軟化点より40〜50℃高い温
度にて紡糸することができ、この紡糸した繊維
は、空気酸化による不融化処理が可能である。そ
してかかる不融化処理後、ArやN2の如き不活性
ガス雰囲気中で約1000℃まで昇温し、焼成炭化す
ることによつて炭素繊維とすることができる。 The precursor pitch thus obtained can be spun at a temperature 40 to 50° C. higher than the softening point using normal melt spinnability, and the spun fibers can be infusible by air oxidation. After such infusibility treatment, carbon fibers can be obtained by raising the temperature to about 1000° C. in an inert gas atmosphere such as Ar or N 2 and sintering and carbonizing.
実施例
タール軟ピツチ（キノリン不溶分〔Q.I〕＝2.4
％）を300℃、60気圧の条件の下に、２倍量のガ
ス軽油で抽出処理して、フリーカーボンを主体と
する高分子量成分を沈降除去し、ついで溶剤を除
去して軟化点：70℃、ベンゼン不溶分：13％、キ
ノリン不溶分：トレースのピツチとした。このピ
ツチを、Ar流量４／minのArバブリングの下
で430℃に５分間保持し、プリカーサーピツチと
した。このプリカーサーピツチの軟化点は232℃、
またベンゼン不溶分：48.5％、キノリン不溶分：
トレースであつた。Example Tar soft pitch (quinoline insoluble [QI] = 2.4
%) under the conditions of 300℃ and 60 atm with twice the amount of gas light oil to remove high molecular weight components, mainly free carbon, by sedimentation, and then remove the solvent to obtain a material with a softening point of 70. °C, benzene insoluble content: 13%, quinoline insoluble content: trace pitch. This pitch was held at 430° C. for 5 minutes under Ar bubbling at an Ar flow rate of 4/min to form a precursor pitch. The softening point of this precursor pitch is 232℃,
Also, benzene insoluble content: 48.5%, quinoline insoluble content:
It was a trace.
得られたプリカーサーピツチを270℃で溶融紡
糸し、ついで290℃で２時間空気酸化したのち、
引続きアルゴン雰囲気中にて1000℃で炭化処理す
ることによつて炭素繊維とした。得られた炭素繊
維の繊維径は11.3μｍ、また引張強度：108Kg／
mm2、弾性率：4.5t／mm2であつた。 The obtained precursor pitch was melt-spun at 270°C, and then air oxidized at 290°C for 2 hours.
Subsequently, carbon fibers were obtained by carbonization treatment at 1000°C in an argon atmosphere. The fiber diameter of the obtained carbon fiber was 11.3μm, and the tensile strength was 108Kg/
mm 2 , elastic modulus: 4.5t/mm 2 .
発明の効果
かくしてこの発明によれば、タールピツチの溶
剤抽出を臨界状態で行うことによつて、フリーカ
ーボンや灰分はいうまでもなく、該ピツチ中に存
在する高分子量成分をも溶剤不溶分として容易に
分離除去でき、かくして紡糸性や不融化性の改善
のために従来必要とされていた水素化処理などの
特殊なピツチ調製を行う必要なしに、炭素繊維プ
リカーサーピツチとして要求される性質の悉くを
付与することができ、有利である。Effects of the Invention Thus, according to the present invention, by performing solvent extraction of tar pitch in a critical state, not only free carbon and ash but also high molecular weight components present in the pitch can be easily converted into solvent-insoluble components. In this way, all the properties required for a carbon fiber precursor pitch can be achieved without the need for special pitch preparation such as hydrogenation treatment, which was conventionally required to improve spinnability and infusibility. It is advantageous that it can be given.
Claims (1)
臨界状態での抽出処理を施して溶剤不溶分を分離
除去したのち、抽出液からさらに溶剤を除去して
フリーカーボンを含まないピツチとし、ついで得
られたピツチに加熱処理を施すことから成る炭素
繊維プリカーサーピツチの製造方法。 ２ 加熱処理が、減圧下または不活性ガスのバブ
リング下における350〜450℃の温度範囲での熱処
理である特許請求の範囲第１項記載の方法。[Scope of Claims] 1 Tar pitch is subjected to extraction treatment in a critical state with an aromatic low-boiling point solvent to separate and remove solvent-insoluble components, and then the solvent is further removed from the extract to produce pitch that does not contain free carbon. A method for producing a carbon fiber precursor pitch, which comprises: and then heat-treating the pitch obtained. 2. The method according to claim 1, wherein the heat treatment is a heat treatment in a temperature range of 350 to 450°C under reduced pressure or under bubbling of inert gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2612784A JPS60170694A (en) | 1984-02-16 | 1984-02-16 | Preparation of precursor pitch of carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2612784A JPS60170694A (en) | 1984-02-16 | 1984-02-16 | Preparation of precursor pitch of carbon fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60170694A JPS60170694A (en) | 1985-09-04 |
| JPH0356599B2 true JPH0356599B2 (en) | 1991-08-28 |
Family
ID=12184895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2612784A Granted JPS60170694A (en) | 1984-02-16 | 1984-02-16 | Preparation of precursor pitch of carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60170694A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6187790A (en) * | 1984-10-05 | 1986-05-06 | Kawasaki Steel Corp | Production of precursor pitch for carbon fiber |
| JPS61162586A (en) * | 1985-01-08 | 1986-07-23 | Kawasaki Steel Corp | Production of precursor pitch for carbon fiber |
| JPS63112687A (en) * | 1986-10-29 | 1988-05-17 | Jgc Corp | Method of fractionating pitch |
| JPS63122787A (en) * | 1986-11-13 | 1988-05-26 | Jgc Corp | Purification of tar pitch |
| JPS6469692A (en) * | 1987-09-09 | 1989-03-15 | Jgc Corp | Method of fractionating tar pitch |
| US5032250A (en) * | 1988-12-22 | 1991-07-16 | Conoco Inc. | Process for isolating mesophase pitch |
| CN104193063B (en) * | 2014-09-16 | 2016-01-27 | 王茜茜 | A kind of tar and waste water treatment unit preparing pitch |
-
1984
- 1984-02-16 JP JP2612784A patent/JPS60170694A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60170694A (en) | 1985-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4578177A (en) | Method for producing a precursor pitch for carbon fiber | |
| JPH0356599B2 (en) | ||
| JPH0670220B2 (en) | Carbon fiber pitch manufacturing method | |
| JPH0321588B2 (en) | ||
| JPS6030365B2 (en) | Method for producing high strength, high modulus carbon fiber | |
| JPS5938280A (en) | Preparation of precursor pitch for carbon fiber | |
| JPH058238B2 (en) | ||
| JPH0150275B2 (en) | ||
| JPS6030366B2 (en) | Manufacturing method for high-strength, high-modulus carbon fiber | |
| JPH0532494B2 (en) | ||
| JPH0150269B2 (en) | ||
| JPS60202189A (en) | Pitch for carbonaceous material and its preparation | |
| JPS6018573A (en) | Preparation of precursor pitch for carbon fiber | |
| JPS60181313A (en) | Manufacture of pitch fiber | |
| JPS5834569B2 (en) | Carbon fiber manufacturing method | |
| JPS6183319A (en) | Carbon fiber and its production | |
| JPH0367123B2 (en) | ||
| JP2594907B2 (en) | Method for producing pitch carbon fiber | |
| JPH0583115B2 (en) | ||
| JPS59155494A (en) | Preparation of pitch material for carbon fiber | |
| JPH0424217A (en) | Production of precursor pitch for general purpose carbon fiber | |
| JP2982406B2 (en) | Method for producing spinning pitch for carbon fiber | |
| JPS58144127A (en) | Preparation of carbon fiber | |
| JPS61138721A (en) | Production of carbon fiber | |
| JPH054435B2 (en) |