JPH0629434B2 - Method for producing mesophase pitch - Google Patents
Method for producing mesophase pitchInfo
- Publication number
- JPH0629434B2 JPH0629434B2 JP62159112A JP15911287A JPH0629434B2 JP H0629434 B2 JPH0629434 B2 JP H0629434B2 JP 62159112 A JP62159112 A JP 62159112A JP 15911287 A JP15911287 A JP 15911287A JP H0629434 B2 JPH0629434 B2 JP H0629434B2
- Authority
- JP
- Japan
- Prior art keywords
- pitch
- weight
- mesophase
- benzene
- quinoline
- 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 - Lifetime
Links
- 239000011302 mesophase pitch Substances 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 99
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 78
- 239000011295 pitch Substances 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 25
- 238000005984 hydrogenation reaction Methods 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 239000002641 tar oil Substances 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 9
- 239000011294 coal tar pitch Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002407 reforming Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011331 needle coke Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Working-Up Tar And Pitch (AREA)
- Inorganic Fibers (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、光学的異方性繊維状組織（流れ構造）を有す
るメソフェーズピッチを簡単かつ有効に製造する方法に
関するものであり、かかるピッチは高品位ニードルコー
クスあるいは高性能炭素繊維等の特殊炭素材料の製造原
料として利用することができる。TECHNICAL FIELD The present invention relates to a method for easily and effectively producing a mesophase pitch having an optically anisotropic fibrous structure (flow structure). It can be used as a raw material for producing high-quality needle coke or special carbon materials such as high-performance carbon fiber.
（従来の技術） 従来、代表的なメソフェーズピッチの製造方法（特公昭
59−3567号公報）は等方性ピッチを熱処理してメソフェ
ーズを発生させる方法である。しかし、この方法で得ら
れるメソフェーズ発生量はキノリン不溶分量にほぼ一致
し、高キノリン不溶分含有メソフェーズピッチとなる。
ピッチの熱処理過程で発生するかかるキノリン不溶分は
それ自身不融、不溶の重縮合化合物であることから、メ
ソフェーズピッチ中のキノリン不溶分の増加はメソフェ
ーズピッチの粘度あるいは溶融温度を増加させる結果、
特にメソフェーズピッチを高性能炭素繊維の原料料とし
て用いる場合、メソフェーズピッチの紡糸性の劣化およ
び溶融温度の上昇による熱安定性の低下要因となる。(Prior Art) Conventionally, a typical mesophase pitch manufacturing method
59-3567) is a method of heat-treating an isotropic pitch to generate a mesophase. However, the amount of mesophase generated by this method is almost the same as the amount of quinoline insoluble matter, resulting in a high quinoline insoluble matter containing mesophase pitch.
Since such quinoline insoluble matter generated in the heat treatment process of pitch is itself infusible and is an insoluble polycondensation compound, an increase in quinoline insoluble matter in mesophase pitch results in an increase in viscosity or melting temperature of mesophase pitch,
In particular, when mesophase pitch is used as a raw material for high-performance carbon fiber, it causes deterioration of the spinnability of mesophase pitch and a decrease in thermal stability due to an increase in melting temperature.
一方、かかる問題点を回避するためにキノリン不溶分含
有量の低いメソフェーズピッチの調製法も工夫され、例
えば特公昭55−58287号および同62−1990号各公報に記
載されているように、適切な原料ピッチを選択し、熱処
理後メソフェーズ化に有効な成分を多く含むピッチを特
定の有機溶媒で抽出し、更に熱処理して25重量％以下の
キノリン不溶分含有メソフェーズピッチが形成されてい
る。その他、ピッチを熱処理して得た部分液晶化ピッチ
から液晶部を抽出あるいは相分離する方法（英国特許公
開明細書第2005298号、特公昭61−31159号）、キノリン
不溶分含有メソフェーズピッチを調製後、水添改質して
可溶化する方法（特公昭58−18421号）あるいはメソフ
ェーズ前駆体を水添改質する方法（特公昭57−100186
号）等により熱溶融性あるいは溶解性の高いメソフェー
ズピッチが調製されている。On the other hand, in order to avoid such problems, a method for preparing mesophase pitch having a low quinoline insoluble content is also devised, and as described in, for example, Japanese Patent Publications No. 55-58287 and No. 62-1990, it is appropriate. After selecting a different raw material pitch, a pitch containing a large amount of components effective for mesophase formation after heat treatment is extracted with a specific organic solvent, and further heat treated to form a mesophase pitch containing 25% by weight or less of quinoline insoluble matter. In addition, a method of extracting or phase-separating a liquid crystal part from a partially liquid crystallized pitch obtained by heat-treating the pitch (British Patent Publication No. 2005298, Japanese Patent Publication No. 61-31159), after preparing a quinoline-insoluble content-containing mesophase pitch , Hydrogenation reforming to solubilize (Japanese Patent Publication No. 58-18421) or hydrogenation reforming of mesophase precursor (Japanese Patent Publication No. 57-100186).
No.) and the like have prepared mesophase pitch having high heat melting property or high solubility.
（発明が解決しようとする問題点） しかしながら、上述の従来法はいずれもその処理が簡便
とはいえず、有効な製造方法とはいえないのが実情であ
る。(Problems to be Solved by the Invention) However, none of the above-mentioned conventional methods is simple in treatment, and is not an effective manufacturing method.
すなわち、前記特公昭55−58287号および同62−1990号
各公報記載の方法はピッチの熱処理を二段階で行う必要
があり、またその他の上記従来法は総じて、生成物であ
るメソフェーズピッチの後処理を必要とする煩雑さがあ
り、いずれも改善の余地があるからである。従って、よ
り有効でかつ簡便な可溶性メソフェーズピッチの製造技
術の確立が望まれている。That is, in the methods described in JP-B-55-58287 and JP-A-62-1990, it is necessary to perform the heat treatment of the pitch in two steps, and the other conventional methods described above are generally after the mesophase pitch of the product. This is because there is complexity that requires treatment and there is room for improvement in both cases. Therefore, establishment of a more effective and convenient manufacturing technique of soluble mesophase pitch is desired.
そこで本発明の目的は、光学的異方性流れ組織を有する
低キノリン不溶分含有メソフェーズピッチを簡便かつ有
効に製造する方法、すなわち生成物である当該メソフェ
ーズピッチの後処理の必要性がなく、かつ一回の熱処理
で完結できる製造方法を提供することにある。Therefore, an object of the present invention is to provide a method for easily and effectively producing low quinoline insoluble content mesophase pitch having an optically anisotropic flow structure, that is, there is no need for post-treatment of the mesophase pitch as a product, and It is to provide a manufacturing method which can be completed by one heat treatment.
（問題点を解決するための手段） 本発明者らは、低キノリン不溶分含有メソフェーズピッ
チの製造に伴う前述の従来技術の問題点を解決するため
に、１）出発原料ピッチの改質、２）メソフェーズ化に
有効な成の調製、３）熱処理方法およびその条件の最適
化を図ることを基本思想に鋭意検討した結果、ある所定
の処理および条件の下で、光学的異方性相が90％以上で
かつキノリン不溶分が30重量％以下であるメソフェーズ
ピッチを従来の製造技術よりも有効かつ簡便に得られる
ことを見い出し本発明を完成するに至った。(Means for Solving Problems) In order to solve the above-mentioned problems of the prior art associated with the production of a low quinoline insoluble content mesophase pitch, the present inventors have: 1) reforming a starting raw material pitch, 2) ) The preparation of a composition effective for the mesophase formation, 3) The earnest study on the basic idea of optimizing the heat treatment method and its conditions. As a result, it was found that the optically anisotropic phase was 90 The inventors have found that mesophase pitch having a quinoline insoluble content of not less than 30% by weight and not more than 30% by weight can be obtained more effectively and simply than conventional manufacturing techniques, and completed the present invention.
すなわち本発明は、１）コールタールピッチをその水添
深度（ピッチ１分子あたり、水添反応によって増加した
水素原子数）が0.3以上となるように水添改質し、 ２）得られた水素化処理ピッチをベンゼン不溶分を40重
量％以上でキノリン不溶分を1.0重量％以下、好ましく
はベンゼン不溶分を60重量％以上でキノリン不溶分をト
レースに調製してメソフェーズ化に有効な成分を多く含
むピッチとし、 ３）得られた調製ピッチを510℃以下の温度で不活性ガ
ス気流下、常圧もしくは減圧下で熱処理することによ
り、光学的異方性相が90以上でかつキノリン不溶分が30
重量％以下であるメソフェーズピッチを後処理工程の必
要性なく製造することを特徴とするものである。That is, according to the present invention, 1) the coal tar pitch is hydrogenated and reformed so that the hydrogenation depth (the number of hydrogen atoms increased by the hydrogenation reaction per pitch molecule) is 0.3 or more, and 2) the obtained hydrogen is obtained. The chemical treatment pitch is 40% by weight or more of benzene and 1.0% by weight or less of quinoline, preferably 60% by weight or more of benzene, and traces of quinoline insoluble matter are prepared to increase the amount of effective components for mesophase formation. 3) By heat-treating the obtained prepared pitch at a temperature of 510 ° C. or less under an inert gas stream under atmospheric pressure or reduced pressure, the optically anisotropic phase is 90 or more and the quinoline insoluble content is 30
It is characterized in that mesophase pitch of not more than wt% is produced without the need for a post-treatment step.
また本発明においては、記メソフェーズ化に有効な成分
を多く含むピッチを熱処理する際、より好ましくは沸点
150〜450℃の芳香族性タール油を共存させることによっ
て熱処理条件を更に厳密に制御して、ピッチの熱覆歴の
均一化および光学的異方性相の展開を図り、目標とする
低キノリン不溶分含有メソフェーズピッチをより容易に
製造せんとするものである。Further, in the present invention, when heat-treating a pitch containing a large amount of components effective for mesophase formation, more preferably the boiling point
By coexisting an aromatic tar oil at 150-450 ℃, the heat treatment conditions can be controlled more strictly to make the thermal history of the pitch uniform and develop the optically anisotropic phase. It is intended to more easily produce an insoluble content-containing mesophase pitch.
（作 用） 本発明において行うコールタールピッチの水素化処理は
従来公知の石油系、石炭系重質油の水添改質に採用され
る種々の方法、例えば水素供与性溶媒を用いる方法、接
触水添法等のいずれの手段を用いても良く、次式、 水添深度＝（Ｈｗｔ％×１２×Ｃｏ／Ｃｗｔ％）−Ｈｏ によって定義されるピッチの水添深度、すなわちピッチ
１分子当り水添処理によって増加した水素原子数が0.3
以上であれば良い。このことは、原料ピッチを含め水添
深度が0.3未満の水素化処理ピッチを本発明の手順に従
って調製し、熱処理しても、キノリン不溶分30重量％以
下の光学的異方性流れ組織を有するメソフェーズピッチ
を形成できないことになる。(Operation) The hydrotreating of coal tar pitch carried out in the present invention is carried out by various methods which are conventionally used for hydrogenation reforming of petroleum-based and coal-based heavy oils, for example, a method using a hydrogen-donating solvent, catalytic treatment. Any means such as a hydrogenation method may be used, and the following equation: Hydrogenation depth = (H wt% × 12 × Co / C wt% ) −Ho The depth of hydrogenation of the pitch defined by, that is, the number of hydrogen atoms increased by hydrogenation treatment per pitch molecule is 0.3.
It is good if it is above. This means that even if a hydrotreated pitch having a hydrogenation depth of less than 0.3 including the raw material pitch is prepared according to the procedure of the present invention and subjected to heat treatment, it has an optically anisotropic flow structure having a quinoline insoluble content of 30% by weight or less. The mesophase pitch cannot be formed.
次に、本発明における水添深度が0.3以上の水素化処理
コールタールピッチから、ベンゼン不溶分40重量％以
上、好ましくは60重量％以上でかつキノリン不溶分１重
量％以下、好ましくはトレースの組成を有するメソフェ
ーズ化に有効な成分を多く含むピッチを調製する方法は
特に限定されるものではないが、例えば、 ｉ）前記水素化処理コールタールピッチから、溶剤分別
により軽質分を除去する、 ii）前記水素化処理コールタールピッチから、蒸留によ
り軽質を除除去する、 iii）前記水素化処理コールタールピッチに同水素化処
理コールタールピッチのベンゼン不溶分に富んだ成分を
添加する、 iv）ｉ）〜iii）のうち２つ以上を組み合わせる、等の
方法によって調製することができる。Next, from the hydrogenated coal tar pitch having a hydrogenation depth of 0.3 or more in the present invention, the benzene insoluble content is 40% by weight or more, preferably 60% by weight or more and the quinoline insoluble content is 1% by weight or less, preferably the composition of the trace. There is no particular limitation on the method for preparing the pitch containing a large amount of the components effective for mesophase formation, which includes, for example, i) removing light fractions from the hydrotreated coal tar pitch by solvent fractionation, ii) Lights are removed from the hydrotreated coal tar pitch by distillation, iii) a component rich in benzene insoluble matter of the hydrotreated coal tar pitch is added, iv) i) ~ Iii) can be prepared by a method of combining two or more.
尚、ｉ）の溶剤分別とは、必ずしも溶剤可溶分と不溶分
とを完全に分離する必要はなく、適量の溶剤を使用して
水素化処理コールタールピッチ中の溶剤可溶成分の一部
を除去する方法も含むものとする。The solvent fraction of i) does not necessarily mean that the solvent-soluble component and the insoluble component need to be completely separated, and an appropriate amount of solvent is used to partially remove the solvent-soluble component in the hydrotreated coal tar pitch. The method of removing is also included.
本発明におけるメソフェーズ化に有効な成分を多く含む
ピッチとは、具体的には前述の如くベンゼン不溶分を少
なくとも40重量％以上、好ましくは60重量％以上でかつ
キノリン不溶分を１．０重量％以下、好ましくはトレー
スに調製したピッチのことであるが、これは次の知見に
基づき求められたものである。The pitch containing a large amount of effective components for mesophase formation in the present invention specifically means at least 40% by weight or more, preferably 60% by weight or more of benzene insoluble matter and 1.0% by weight of quinoline insoluble matter as described above. Hereinafter, the pitch is preferably adjusted to be a trace, which is obtained based on the following findings.
第１図に示す如く光学的異方性相の展開量がメソフェー
ズピッチ中のベンゼン不溶分量（ＢＩ）と相関性を有
し、約60重量％以上において光学的異方性相の展開量が
急激に増加し、ベンゼン不溶分が90重量％以上では光学
的異方性相が95〜100％の全面光学的異方性流れ組織を
形成することを見い出した。従って、原料ピッチ中のベ
ンゼン不溶分量の初期値が大きいほど光学的異方性相の
展開には優利であるが、ピッチの熱処理過程では熱重縮
合反応と軽質分の留出が同時に生起し、ベンゼン不溶分
量の増大が図れるため、原料ピッチ中の初期ベンゼン不
溶分量を90重量％以上に上げる必要はなく、実際的には
第２図より明らかな如く40重量％以上、より好ましくは
60重量％以上に調製すれば良いことが判明した。更に
は、熱処理過程において発生するキノリン不溶分（Ｑ
Ｉ）は光学的異方性相の展開量と相関性がなく、かつ原
料ピッチ中のベンゼン不溶分量の初期値が大きくなるほ
ど、低下することを見い出した（第３図）。As shown in Fig. 1, the expansion amount of the optically anisotropic phase has a correlation with the benzene insoluble content (BI) in the mesophase pitch, and the expansion amount of the optically anisotropic phase is abrupt at about 60 wt% or more. It was found that when the content of benzene insolubles is more than 90% by weight, the optically anisotropic phase forms a fully optically anisotropic flow structure of 95 to 100%. Therefore, the larger the initial value of the benzene insoluble content in the raw material pitch is, the more advantageous it is for the development of the optically anisotropic phase, but in the heat treatment process of the pitch, the thermal polycondensation reaction and the distillation of the light fraction occur simultaneously, Since the amount of benzene insoluble matter can be increased, it is not necessary to raise the initial amount of benzene insoluble matter in the raw material pitch to 90% by weight or more. In practice, as shown in FIG.
It was found that the amount should be adjusted to 60% by weight or more. Furthermore, the quinoline insoluble matter (Q
It has been found that I) has no correlation with the development amount of the optically anisotropic phase, and decreases as the initial value of the benzene insoluble content in the raw material pitch increases (FIG. 3).
かかる知見に基づき上記方法によって改質調製したメソ
フェーズ化に有効な成分を多く含むピッチを熱処理する
場合、光学的異方性相の量を90％以上に保ちつつ、キノ
リン不溶分の発生量を30重量％以下の範囲に制御するた
めには反応温度、反応圧力、昇温速度等の熱処理条件を
厳密に制御することが肝要であり、具体的には前記ピッ
チに510℃以下の温度で不活性ガスを吹き込み、常圧も
しくは減圧下で短時間熱処理することが不可欠である。Based on such findings, when heat-treating a pitch containing a large amount of effective components for mesophase formation modified by the above method, the amount of quinoline-insoluble matter generated was 30% while maintaining the amount of the optically anisotropic phase at 90% or more. It is important to strictly control the heat treatment conditions such as the reaction temperature, the reaction pressure, and the heating rate in order to control the content in the range of not more than wt%. Specifically, the pitch is inert at a temperature of 510 ° C or less. It is indispensable to blow gas and perform heat treatment for a short time under normal pressure or reduced pressure.
また本発明においては、より好ましくは熱処理時に上述
のメソフェーズ化に有効な成分を多含むピッチに常圧沸
点150〜450℃の芳香族性タール油を添加して熱処理する
が、これはピッチ中のベンゼン不溶分量が増加するとピ
ッチの熱溶融性が低下し、熱処理過程でのピッチの熱覆
歴の不均一化および液晶分子の配向性の低下が起こり、
均一な光学的異方性流れ組織の形成が阻外されるので、
これを回避するためである。すなわち、常圧沸点150〜4
50℃の芳香族性タール油の添加は、ピッチ中のベンゼン
不溶分を熱処理過程で均一に溶解させる役割を有するこ
とに基づくものである。この結果、かかる芳香族性ター
ル油の添加は、本発明におけるメソフェーズ化に有効な
成分を多く含むピッチのように高いベンゼン不溶分含有
ピッチでも第４図に示すように均一に昇温加熱すること
を可能ならしめ、かつ光学的異方性流れ組織の発生を阻
外することなく光学的異方性相を90％以上でかつキノリ
ン不溶分を30重量％以下のメソフェーズピッチを抽出あ
るいは相分離等の後処理工程なしに一段階の熱処理工程
でより簡便に得ることを可能ならしめるものである。Further, in the present invention, more preferably the aromatic tar oil having a normal pressure boiling point of 150 to 450 ° C. is added to the pitch containing many components effective for the above-mentioned mesophase during the heat treatment, and the heat treatment is performed. When the amount of benzene-insoluble matter increases, the thermal melting property of the pitch decreases, and the thermal covering history of the pitch becomes nonuniform during the heat treatment and the orientation of the liquid crystal molecules decreases,
Since formation of a uniform optically anisotropic flow structure is prevented,
This is to avoid this. That is, normal pressure boiling point 150 to 4
The addition of the aromatic tar oil at 50 ° C. is based on the fact that it has the role of uniformly dissolving the benzene-insoluble matter in the pitch during the heat treatment process. As a result, the addition of such an aromatic tar oil should be carried out by uniformly heating up the temperature as shown in FIG. 4 even with a pitch containing a high benzene-insoluble content such as a pitch containing a large amount of components effective for mesophase formation in the present invention. The mesophase pitch of 90% or more of optically anisotropic phase and 30% by weight or less of quinoline insoluble matter is extracted or phase separation without disturbing the generation of optically anisotropic flow structure. This makes it possible to obtain it more easily by a one-step heat treatment process without a post-treatment process.
（実施例） 次に本発明を実施例により具体的に説明する。(Examples) Next, the present invention will be specifically described with reference to Examples.
実施例１ 水添深度が1.9の水素化処理ピッチ（ベンゼン不溶分
量：7.1重量％、キノリン不溶分量：トレース）に、同
ピッチのベンゼン不溶分を更に添加して均一に混合し、
ベンゼン不溶分を75重量％、キノリン不溶分をトレース
に調製した。次いでこの調製ピッチ20gと常圧沸点150〜
400℃の芳香族性タール油20gとを均一に混合し、しかる
後、Ｎ２気流下常圧にて室温から４５５℃まで２℃／分
の速度で昇温した後急冷して、光学的異方性流れ組織が
100％でかつキノリン不溶分を15重量％含有するメソフ
ェーズピッチを得た。Example 1 To a hydrotreated pitch having a hydrogenation depth of 1.9 (benzene insoluble content: 7.1% by weight, quinoline insoluble content: trace), a benzene insoluble content of the same pitch was further added and uniformly mixed,
75% by weight of benzene insoluble matter and quinoline insoluble matter were prepared as traces. Next, this prepared pitch 20 g and normal pressure boiling point 150-
20 g of aromatic tar oil at 400 ° C. was uniformly mixed, and thereafter, the temperature was raised from room temperature to 455 ° C. at a rate of 2 ° C./min at normal pressure under N 2 stream, followed by rapid cooling to obtain an optical difference. The unidirectional flow organization
A mesophase pitch containing 100% by weight and containing 15% by weight of the quinoline insoluble matter was obtained.
実施例２ 水添深度が0.4の水素化処理ピッチ（ベンゼン不溶量：
9.5重量％、キノリン不溶分量：トレース）100ｇとベン
ゼン２とを室温で均一に混合した後、濾過、乾燥して
得た濃縮ピッチ（ベンゼン不溶60重量％含有）を再度ベ
ンゼン２と混合し、濾過、乾燥してベンゼン不溶分を
80重量％、キノリン不溶分を0.5重量％以下に調製し
た。次いでこの調製ピッチ20ｇをＮ２気流下常圧にて室
温から450℃まで２℃／分の速度で昇温した後急冷し
て、光学的異方性流れ組織が100％でかつキノリン不溶
分を26重量％含有すするメソフェーズピッチを得た。Example 2 Hydrotreated pitch with a hydrogenation depth of 0.4 (benzene insoluble content:
9.5 wt%, quinoline insoluble content: trace) 100 g and benzene 2 were uniformly mixed at room temperature, and then filtered and dried to obtain concentrated pitch (containing 60 wt% benzene insoluble), which was mixed again with benzene 2 and filtered. , Dry to remove benzene insoluble matter
80% by weight and quinoline insoluble content were adjusted to 0.5% by weight or less. Next, 20 g of the prepared pitch was heated from room temperature to 450 ° C. at a rate of 2 ° C./min under normal pressure under N 2 gas flow and then rapidly cooled to obtain 100% optically anisotropic flow structure and quinoline insoluble matter. A mesophase pitch containing 26% by weight was obtained.
実施例３ 水添深度が5.1の水素化処理ピッチ（ベンゼン不溶分
量：4.8重量％、キノリン不溶分量：トレース）を300
℃、４mmHgの減圧下で蒸留して軽質分を減少させた濃縮
ピッチに、更に同水素化処理ピッチ中のベンゼン不溶分
を添加して均一に混合し、ベンゼン不溶分を80重量％、
キノリン不溶分をトレースに調製した。次いで、この調
製ピッチ20ｇと常圧沸点150〜400℃の芳香族性タール油
20ｇとを均一に混合し、しかる後Ｎ２気流下常圧にて室
温から450℃まで２℃／分の速度で昇温した後急冷し
て、光学的異方性流れ組織が100％でかつキノリン不溶
分を6.5重量％含有するメソフェーズピッチを得た。Example 3 300 hydrogenated pitches having a hydrogenation depth of 5.1 (benzene insoluble content: 4.8% by weight, quinoline insoluble content: trace) were used.
Benzene insoluble matter in the same hydrotreated pitch was further added to the concentrated pitch reduced in lightness by distilling under reduced pressure at 4 ° C and 4 mmHg, and mixed uniformly to obtain 80% by weight of benzene insoluble matter.
Quinoline insolubles were prepared in traces. Next, 20 g of this prepared pitch and an aromatic tar oil having a boiling point of 150 to 400 ° C at atmospheric pressure
20 g were mixed uniformly, and then the temperature was raised from room temperature to 450 ° C. at a rate of 2 ° C./min at normal pressure under N 2 flow and then rapidly cooled to obtain 100% optically anisotropic flow structure. A mesophase pitch containing 6.5% by weight of quinoline insoluble matter was obtained.
実施例４ 実施例３において調製したピッチと芳香族性タール油と
の混合物40gを室温から440℃まで２℃／分の速度で昇温
した後急冷して、光学的異方性流れ組織が92％でかつキ
ノリン不溶分がトレースのメソフェーズピッチを得た。Example 4 40 g of the mixture of pitch and aromatic tar oil prepared in Example 3 was heated from room temperature to 440 ° C. at a rate of 2 ° C./min and then rapidly cooled to obtain an optically anisotropic flow structure of 92. % And the quinoline insoluble matter gave mesophase pitch of trace.
実施例５ 水添深度が5.1の水素化処理ピッチ（ベンゼン不溶分
量：4.8重量％、キノリン不溶分量：トレース）100ｇに
アセトン４を加え、アセトン還流下１時間放置した
後、濾過、乾燥して得た濃縮ピッチ（ベンゼン不溶分含
有量40重量％）に、更に同水素化処理ピッチ中のトルエ
ン不溶分を添加して、ベンゼン不溶分を60重量％、キノ
リン不溶分をトレースに調製した。次いで、この調製ピ
ッチ20gと常圧沸点150〜450℃の芳香族性タール油20gと
を均一に混合した後、Ｎ２気流下、10mmHgの減圧下で室
温から450℃まで２℃／分の速度で昇温した後冷して、
光学的異方性流れ組織が100％でかつキノリン不溶分を1
1重量％含有するメソフェーズピッチを得た。Example 5 Acetone 4 was added to 100 g of a hydrogenated pitch having a hydrogenation depth of 5.1 (benzene insoluble content: 4.8% by weight, quinoline insoluble content: trace), and the mixture was allowed to stand for 1 hour under acetone refluxing, filtered and dried to obtain Toluene insoluble matter in the same hydrotreated pitch was further added to the concentrated pitch (benzene insoluble matter content 40% by weight) to prepare benzene insoluble matter as 60% by weight and quinoline insoluble matter as traces. Then, 20 g of this prepared pitch and 20 g of aromatic tar oil having a boiling point of 150 to 450 ° C. at normal pressure are uniformly mixed, and then at a rate of 2 ° C./minute from room temperature to 450 ° C. under a reduced pressure of 10 mmHg under N 2 flow. And then cool down,
Optically anisotropic flow structure 100% and quinoline insoluble matter 1
A mesophase pitch containing 1% by weight was obtained.
比較例１ 水添深度が1.9の水素化処理ピッチ（ベンゼン不溶分
量：7.1重量％、キノリン不溶分量：トレース）１００
ｇとアセトン２とを室温で均一に混合した後、濾過、
乾燥して得た濃縮ピッチ（ベンゼン不溶分33重量％含
有）20ｇと常圧沸点150〜400℃の芳香族性タール油20ｇ
とを均一に混合した。次いで、この混合物Ｎ２気流下、
常圧にて室温から510℃まで２℃／分の速度で昇温した
後急冷して、光学的異方性流れ組織が97.7％のメソフェ
ーズピッチを得たが、キノリン不溶分は55.7重量％であ
った。Comparative Example 1 Hydrogenated pitch with a hydrogenation depth of 1.9 (benzene insoluble content: 7.1% by weight, quinoline insoluble content: trace) 100
g and acetone 2 were uniformly mixed at room temperature, then filtered,
20 g of concentrated pitch (containing 33% by weight of benzene-insoluble matter) obtained by drying and 20 g of aromatic tar oil having a boiling point of 150 to 400 ° C at atmospheric pressure
And were mixed uniformly. Then, under a N 2 stream of this mixture,
The temperature was raised from room temperature to 510 ° C at normal pressure at a rate of 2 ° C / min and then rapidly cooled to obtain mesophase pitch with an optically anisotropic flow structure of 97.7%, but the quinoline insoluble content was 55.7% by weight. there were.
比較例２ 水添深度が5.1の水素化処理ピッチ（ベンゼン不溶分
量：4.8重量％、キノリン不溶分量：トレース）１００
ｇとアセトン２とを室温で均一に混合した後、濾過、
乾燥して得た濃縮ピッチ（ベンゼン不溶分37重量％含
有）20ｇと常圧沸点150〜400℃の芳香族性タール油20ｇ
とを均一に混合した。次いで、この混合物をＮ２気流
下、常圧にて室温から510℃まで２℃／分の速度で昇温
した後急冷して、光学的異方性流れ組織が100％のメソ
フェーズピッチを得たが、キノリン不溶分は35重量％で
あった。Comparative Example 2 Hydrogenated pitch with a hydrogenation depth of 5.1 (benzene insoluble content: 4.8% by weight, quinoline insoluble content: trace) 100
g and acetone 2 were uniformly mixed at room temperature, then filtered,
20 g of concentrated pitch (containing 37% by weight of benzene insolubles) obtained by drying and 20 g of aromatic tar oil having a boiling point of 150 to 400 ° C at atmospheric pressure
And were mixed uniformly. Next, this mixture was heated at a rate of 2 ° C./min from room temperature to 510 ° C. at normal pressure under N 2 gas flow and then rapidly cooled to obtain a mesophase pitch having 100% optically anisotropic flow structure. However, the quinoline insoluble content was 35% by weight.
比較例３ 水添深度が5.1の水素化処理ピッチ（ベンゼン不溶分
量：4.8重量％、キノリン不溶分量：トレース）２０ｇ
をＮ２気流下、４mmHｇの減圧下で２℃／分の昇温速度
で室温から480℃まで昇温した後急冷して、光学的異方
性流れ組織が100％のメソフェーズピッチを得たが、キ
ノリン不溶分は40.5重量％であった。Comparative Example 3 Hydrogenated pitch having a hydrogenation depth of 5.1 (benzene insoluble content: 4.8% by weight, quinoline insoluble content: trace) 20 g
Was heated at room temperature to 480 ° C. at a heating rate of 2 ° C./min under a reduced pressure of 4 mmHg under N 2 gas flow and then rapidly cooled to obtain a mesophase pitch having an optically anisotropic flow structure of 100%. The quinoline insoluble content was 40.5% by weight.
（発明の効果） 以上説明してきたように本発明のメソフェーズピッチの
製造方法においては、従来の製造技術よりもより有効で
かつ簡便に可溶性でＱＩが30重量％以下のメソフェーズ
ピッチを製造することができ、すなわち成物であるメソ
フェーズピッチの抽出あるいは相分離などの後処理工程
の必要性がなく、かつ１回の熱処理により、光学的異方
性流れ組織が90％以上でキノリン不溶分を30重量％以下
しか含有しないメソフェーズピッチを製造することがで
き、産業上の有用性がある。(Effects of the Invention) As described above, in the method for producing mesophase pitch of the present invention, it is possible to produce mesophase pitch having a QI of 30% by weight or less, which is more effective and easier than conventional production techniques. Yes, that is, there is no need for post-treatment steps such as extraction of mesophase pitch or phase separation, which is a product, and a single heat treatment has an optically anisotropic flow structure of 90% or more and a quinoline insoluble content of 30% by weight. A mesophase pitch containing only less than 50% can be produced, which is industrially useful.
第１図はメソフェーズピッチのベンゼン不溶分量（Ｂ
Ｉ）と光学的異方性分率との関係を示すグラフ、 第２図は原料ピッチのベンゼン不溶分量（ＢＩ）と光学
的異方性相分率との関係を示すグラフ、 第３図は原料ピッチのベンゼン不溶分量（ＢＩ）と100
％光学的異方性メソフェーズピッチのキノリン不溶分量
（ＱＩ）との関係を示すグラフ、 第４図はメソフェーズ化に有効な成分を多く含むピツチ
の時間と温度との関係に基づく昇温曲線を示すグラフで
ある。Figure 1 shows the amount of benzene insoluble matter (B
2) is a graph showing the relationship between I) and the optical anisotropy fraction, FIG. 2 is a graph showing the relationship between the benzene insoluble content (BI) of the raw material pitch and the optically anisotropic phase fraction, and FIG. Benzene insoluble content (BI) of raw material pitch and 100
Fig. 4 is a graph showing the relationship between the% optically anisotropic mesophase pitch and the quinoline insoluble content (QI). Fig. 4 shows the temperature rise curve based on the relationship between time and temperature of a pitch containing a large amount of components effective for mesophase formation. It is a graph.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ１０Ｃ 3/04 Ｆ 6958−4Ｈ 3/10 6958−4Ｈ // Ｄ０１Ｆ 9/145 7199−3Ｂ (72)発明者 杉辺 英孝 千葉県千葉市川崎町１番地 川崎製鉄株式 会社技術研究本部内 (72)発明者 神下 護 千葉県千葉市川崎町１番地 川崎製鉄株式 会社技術研究本部内 (72)発明者 長沢 健 千葉県千葉市川崎町１番地 川崎製鉄株式 会社技術研究本部内 (72)発明者 庄野 弘晃 福島県福島市伏拝字沼の上２−532─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI technical display location C10C 3/04 F 6958-4H 3/10 6958-4H // D01F 9/145 7199-3B (72 ) Inventor Hidetaka Suganabe 1 Kawasaki-cho, Chiba-shi, Chiba Prefecture Technical Research Headquarters, Kawasaki Steel Co., Ltd. Ken Nagasawa 1 Kawasaki-cho, Chiba-shi, Chiba Kawasaki Steel Co., Ltd. Technical Research Headquarters (72) Inventor Hiroaki Shono 2-532 Numaue, Fushijima, Fukushima-shi, Fukushima Prefecture
Claims (2)
ノリン不溶分分が30重量％以下であるメソフェーズピッ
チの製造方法において、 水添深度が0.3以上の水素化処理コールタールピッチか
らベンゼン不溶分40重量％以上でかつキノリン不溶分１
重量％以下の組成を有するピッチを調製し、次いでこの
調製ピッチに510℃以下の温度で不活性ガスを吹き込
み、常圧もしくは減圧下で短時間熱処理することを特徴
とするメソフェーズピッチの製造方法。1. A method for producing mesophase pitch containing 90% or more of an optically anisotropic phase and 30% by weight or less of quinoline-insoluble content, wherein a hydrogenated coal tar pitch having a hydrogenation depth of 0.3 or more is used. To 40% by weight or more of benzene insoluble matter and 1 quinoline insoluble matter
A process for producing a mesophase pitch, which comprises preparing a pitch having a composition of not more than wt% and then blowing an inert gas into the prepared pitch at a temperature of 510 ° C. or less and heat-treating at a normal pressure or a reduced pressure for a short time.
〜450℃の芳香族性タール油を共存させる特許請求の範
囲第１記載の製造方法。2. A boiling point of 150 when heat-treating the prepared pitch.
The production method according to claim 1, wherein an aromatic tar oil having a temperature of 450 ° C. coexists.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62159112A JPH0629434B2 (en) | 1987-06-26 | 1987-06-26 | Method for producing mesophase pitch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62159112A JPH0629434B2 (en) | 1987-06-26 | 1987-06-26 | Method for producing mesophase pitch |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS644693A JPS644693A (en) | 1989-01-09 |
| JPH0629434B2 true JPH0629434B2 (en) | 1994-04-20 |
Family
ID=15686505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62159112A Expired - Lifetime JPH0629434B2 (en) | 1987-06-26 | 1987-06-26 | Method for producing mesophase pitch |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0629434B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102392328B (en) * | 2011-08-29 | 2013-07-10 | 云南昆钢煤焦化有限公司 | Method for intensively producing carbon fiber raw material by coal pitch needle coke |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54160427A (en) * | 1977-07-08 | 1979-12-19 | Exxon Research Engineering Co | Production of optically anisotropic* deformable pitch* optical anisotropic pitch* and pitch fiber |
| JPS6030365A (en) * | 1983-07-28 | 1985-02-15 | Canon Inc | Recorder |
-
1987
- 1987-06-26 JP JP62159112A patent/JPH0629434B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54160427A (en) * | 1977-07-08 | 1979-12-19 | Exxon Research Engineering Co | Production of optically anisotropic* deformable pitch* optical anisotropic pitch* and pitch fiber |
| JPS6030365A (en) * | 1983-07-28 | 1985-02-15 | Canon Inc | Recorder |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS644693A (en) | 1989-01-09 |
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