JPH03277690A - Preparation of binder pitch for use in carbon materials - Google Patents
Preparation of binder pitch for use in carbon materialsInfo
- Publication number
- JPH03277690A JPH03277690A JP7559590A JP7559590A JPH03277690A JP H03277690 A JPH03277690 A JP H03277690A JP 7559590 A JP7559590 A JP 7559590A JP 7559590 A JP7559590 A JP 7559590A JP H03277690 A JPH03277690 A JP H03277690A
- Authority
- JP
- Japan
- Prior art keywords
- pitch
- solvent
- coal tar
- softening point
- binder
- 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
- 239000011305 binder pitch Substances 0.000 title claims abstract description 25
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 51
- 239000011295 pitch Substances 0.000 claims abstract description 27
- 238000000605 extraction Methods 0.000 claims abstract description 22
- 239000011294 coal tar pitch Substances 0.000 claims abstract description 20
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 7
- 238000003763 carbonization Methods 0.000 claims abstract description 5
- 239000011280 coal tar Substances 0.000 claims abstract description 5
- 239000003245 coal Substances 0.000 claims abstract description 3
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000009835 boiling Methods 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 3
- 239000003849 aromatic solvent Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052799 carbon Inorganic materials 0.000 abstract description 14
- 239000011347 resin Substances 0.000 abstract description 14
- 229920005989 resin Polymers 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 5
- 238000004821 distillation Methods 0.000 abstract description 3
- 239000012188 paraffin wax Substances 0.000 abstract description 2
- 239000011302 mesophase pitch Substances 0.000 abstract 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 239000011338 soft pitch Substances 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 238000010304 firing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000011271 tar pitch Substances 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 238000002303 thermal reforming Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000006253 pitch coke Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000010979 ruby Substances 0.000 description 1
- 229910001750 ruby Inorganic materials 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、人造黒鉛電極やアルミ精錬用電極、あるいは
高密度炭素材ｆ１なとに使用されるバインダー用ピッチ
の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing pitch for a binder used for artificial graphite electrodes, aluminum refining electrodes, or high-density carbon material f1.
炭素キイの一般的製造方法としては、粒度調整したピッ
チコークスとバインダー用ピッチとを混練後成形し、焼
成、黒鉛化を行う。この焼成工程ではピッチ中の軽質成
分が揮散し炭素材中に多くの気孔を残すため、焼成後、
含浸ピッチを含浸し、再焼成する工程を数回繰り返して
密度強度を向上させている。このような現状からバイン
ダーピッチの炭化率を向上させ粘結成分を増加させるこ
とが要望されている。A general method for manufacturing carbon keys is to knead pitch coke whose particle size has been adjusted and pitch for a binder, then shape the resulting mixture, followed by firing and graphitization. In this firing process, the light components in the pitch volatilize and leave many pores in the carbon material, so after firing,
The process of impregnating with impregnated pitch and re-firing is repeated several times to improve density strength. Under these circumstances, it is desired to improve the carbonization rate of the binder pitch and increase the caking component.
一般に固定炭素（Ｆ Ｃ）が高くなると炭化率も高くな
るという相関があるため、この固定炭素（ＦＣ）がピッ
チの炭化率を評価する重要な指標として用いられている
。さらにトルエン不溶分（Ｔりからキノリン不溶分（Ｑ
１）を減じた値はβレジンと呼ばれ、その値が大きいほ
ど粘結性が高いのでβレジン含有量の多いピッチが好ま
しい。Generally, there is a correlation that the higher the fixed carbon (FC) is, the higher the carbonization rate is, so this fixed carbon (FC) is used as an important index for evaluating the carbonization rate of pitch. In addition, toluene insoluble matter (Tri) and quinoline insoluble matter (Q
The value obtained by subtracting 1) is called β-resin, and the larger the value, the higher the caking property, so a pitch with a high β-resin content is preferable.
通常、バインダーピッチの原料としては、軟ピツチが使
用されている。軟ピツチは石炭を乾留して生成するコー
ルタールが原料となり、これを常法により常圧蒸留及び
減圧蒸留を行い、運転条件によって軟化点が７０℃以下
に調整されたものである。しかし軟ピツチは固定炭素や
βレジン含有量が低いため、種々の改質操作を加える必
要があり、通常、用途に応じて３００〜４００℃で２〜
２４時間熱改質を行った後、軟化点を調整して製造され
る。熱改質反応は、重合反応の進行に伴いメソフェース
を生成し易いという特徴をもっている。バインダー中の
メソフェースは流動性を阻害したり、焼成電極の組織上
に欠陥を生じさせ、クラックの発生原因になったりする
ため、メソフェースが含まれないよう加熱条件を制御し
て製造される。Usually, soft pitch is used as a raw material for binder pitch. The raw material for soft pitch is coal tar produced by carbonizing coal, which is subjected to normal pressure distillation and vacuum distillation using conventional methods, and its softening point is adjusted to 70° C. or lower depending on the operating conditions. However, since soft pitch has a low fixed carbon and β-resin content, it is necessary to add various modification operations, and it is usually treated at 300 to 400℃ for 2 to 30 minutes depending on the application.
After thermal modification for 24 hours, the softening point is adjusted and manufactured. A thermal reforming reaction is characterized by the tendency to generate mesophase as the polymerization reaction progresses. Mesophase in the binder impedes fluidity, causes defects in the structure of the fired electrode, and causes cracks, so the heating conditions are controlled to avoid mesophase in the binder.
また、熱処理条件を厳しくしたり、ピッチ中の軽質留分
を留去すると軟化点が上昇し、その結果、固定炭素やβ
レジン含有量が多くなる。軟化点が高すぎると、現状の
混線温度ではフィラーとの濡れ性が悪くなるので、混練
工程での温度を高くする必要があるが現在の電極製造工
程では適用が困難である。そのため、軟化点は現状の８
０〜２００℃のままで固定炭素及びβレジン含有量の高
いピッチの製造が望まれる。In addition, if the heat treatment conditions are made stricter or the light fractions in the pitch are distilled off, the softening point increases, and as a result, fixed carbon and β
The resin content increases. If the softening point is too high, the wettability with the filler will be poor at the current mixing temperature, so it is necessary to raise the temperature in the kneading process, but this is difficult to apply in the current electrode manufacturing process. Therefore, the current softening point is 8.
It is desired to produce pitch with a high fixed carbon and beta resin content at a temperature of 0 to 200°C.
これらの問題を解決するため、従来、種々の方法が提案
されている。コールタ−ルビ・ソチに脂肪族溶媒と芳香
族溶媒の混合溶媒を混合して不溶性沈殿物（Ｑ１）を生
成させて、これを分離、除去して、溶解成分を熱改質し
、重質油分を除去することでβレジン留分を増加させる
方法（特公昭６０−３４５９９号公報）、化学反応を利
用した方法としてアルキル化法（特公昭４９−３４７３
２号公報、特開昭６２−２２０５８２号公報）、酸化法
（持分１１／１４９−２０７６０号公報、特開昭５９−
２１５３８７号公報）、硫酸処理法（特開昭６１．−１
３０３９１号公報）、水素添加法（特開昭５８−１８４
２１号公報、特開昭６０−２３８３９３号公報）などが
ある。Various methods have been proposed to solve these problems. A mixed solvent of an aliphatic solvent and an aromatic solvent is mixed with coal tar ruby sochi to form an insoluble precipitate (Q1), which is separated and removed, the dissolved components are thermally modified, and the heavy oil is extracted. (Japanese Patent Publication No. 60-34599), alkylation method (Japanese Patent Publication No. 49-3473) using chemical reactions.
2 Publication No. 11/149-20760, Japanese Patent Application Laid-open No. 1982-220582), oxidation method (Kiken No. 11/149-20760, Japanese Patent Application Laid-open No. 1982-20760)
215387), sulfuric acid treatment method (Unexamined Japanese Patent Publication No. 1983-1)
30391), hydrogenation method (JP-A-58-184)
21, JP-A No. 60-238393), etc.
これらの方法は、［ｔな製造］ニ稈を必要としたり、多
量の副資材を使用したりするものであり必ずしも紅済的
な手法であるとは言えない。These methods require two culms or use a large amount of auxiliary materials, so they cannot necessarily be said to be economical methods.
特１ｍ ｌＩ＃ ６３ ］ ］、 ２６８７ 号公Ｗ
ハタールｔ：” ッチをキノリン不溶分（Ｑ１）とベ
ンゼン可溶分（ＢＳ）と、ベンゼンに不溶でキノリンに
可溶な（Ｂｌ−ＱＳ成分・・・βレジン）に分別する方
法である。特開昭６３−１２２７８７号公報はタールピ
ッチ中のＱｌとＮａ分を除去する方法である。Special 1ml # 63] ], No. 2687 W
This is a method of separating Hatar T:'' into a quinoline-insoluble component (Q1), a benzene-soluble component (BS), and a benzene-insoluble component but a quinoline-soluble component (Bl-QS component...β resin). JP-A-63-122787 discloses a method for removing Ql and Na from tar pitch.
特開昭６４−６９６９２号公報はタールピッチからＱｌ
を除去すると共に、Ｂｌ・ＱＳ成分を多く含むピッチと
、Ｂｌを実質的に含まないピッチとに分画する方法であ
る。何れも超臨界溶剤分別法を採用しているが、タール
ピッチ中の軽質留分を適度に抽出し、抽残ピッチの軟化
点が８０〜２００℃になるようにＱｌを含むピッチを抽
残として抜きとって、バインダーピッチとして使用する
という思想はない。JP-A-64-69692 discloses Ql from tar pitch.
In this method, pitches are divided into pitches containing a large amount of Bl/QS components and pitches that substantially do not contain Bl. In both cases, the supercritical solvent fractionation method is adopted, but the light fraction in the tar pitch is appropriately extracted, and pitch containing Ql is used as raffinate so that the softening point of the raffinate pitch is 80 to 200°C. There is no concept of extracting it and using it as binder pitch.
本発明は複雑な製造二り程や、多量の副資材を使用せず
、極めてシンプルかつ安価な方法で固定炭素が高く、β
レジン含有量が高く、かつメソフエスの生成がないバイ
ンダーピッチを製造する方法を提１」（することをｉｌ
的とする。The present invention does not involve complicated manufacturing steps or use a large amount of auxiliary materials, and is an extremely simple and inexpensive method that produces high fixed carbon and β
We propose a method for producing a binder pitch with a high resin content and no generation of mesophase.
target
本発明は、石炭タールピッチとパラフィン系炭化水素溶
剤または芳香族系炭化水素溶剤を抽出域に装入し、溶剤
の臨界温度〜３７０ ”Ｃの温度、溶剤の臨界圧力〜１
００ｋｇ／ｃｊＧの圧力及び溶剤／石炭タールピッチの
重量ｌｔＯ，５〜６．０の範囲の条件下に保持し、石炭
タールピッチ中の軽質留分を抽出除去することを特徴と
する炭素材用バインダーピッチの製造方法である。The present invention involves charging coal tar pitch and a paraffinic hydrocarbon solvent or an aromatic hydrocarbon solvent into an extraction zone, at a temperature of the critical temperature of the solvent ~370''C, and a critical pressure of the solvent ~1
A binder for carbon materials characterized by extracting and removing light fractions in coal tar pitch by holding it under conditions of a pressure of 00 kg/cjG and a solvent/coal tar pitch weight ltO of 5 to 6.0. This is a method for manufacturing pitch.
石炭タールピッチは任意のものを使用できるが、石炭乾
留時に副生するコールタールを蒸留して得られる軟化点
７０℃以下、キノリン不溶分が０．５〜７． ０！Ｉ！
ｆｆｔ％の軟ピツチが好適である。Any coal tar pitch can be used, but it should have a softening point of 70°C or less and a quinoline insoluble content of 0.5 to 7. 0! I!
A soft pitch of fft% is preferred.
このキノリン不溶分は炭素材の機械強度に影響を及ばず
重要な因子であり、キノリン不溶分を含まないピッチを
炭素材製造用バインダーピッチとして使用すると、必要
とする炭素材の機械強度を確保することができない。従
って原料軟ピツチの軽質留分を除去した後のキノリン不
溶分濃度が所望の値となるものを選択することが望まし
い。This quinoline insoluble content is an important factor that does not affect the mechanical strength of the carbon material, and if pitch that does not contain quinoline insoluble content is used as a binder pitch for carbon material production, the required mechanical strength of the carbon material can be secured. I can't. Therefore, it is desirable to select a material that gives a desired concentration of quinoline insoluble matter after removing the light fraction from the raw material soft pitch.
用いる溶剤は、臨界温度３７０℃以下、好ましくは３６
０℃以下、沸点２００℃以下のものを使用できるが、パ
ラフィン系炭化水素としてはへキサン、ヘプタン及びオ
クタン、芳香族系炭化水素としてはベンゼン、トルエン
、及びキシレンが軟ピツチに対する抽出性能からみて好
適である。The critical temperature of the solvent used is 370°C or lower, preferably 36°C.
Those with a boiling point of 0°C or lower and a boiling point of 200°C or lower can be used, but hexane, heptane, and octane are preferred as paraffin hydrocarbons, and benzene, toluene, and xylene are preferred as aromatic hydrocarbons in terms of extraction performance for soft pitch. It is.
この溶剤の混合割合は、溶剤／石炭タールピッチが０．
５〜６．０以下が好ましい。The mixing ratio of this solvent is such that solvent/coal tar pitch is 0.
5 to 6.0 or less is preferable.
溶剤／石炭タールピッチが６．０より高くなると溶剤回
収と抽出温度までの昇温のエネルギーコストが高くなり
、また、０．５より低いと軽質留分の抽出除去が不十分
になるという問題が生じる。When the solvent/coal tar pitch is higher than 6.0, the energy cost for recovering the solvent and raising the temperature to the extraction temperature becomes high, and when it is lower than 0.5, there is a problem that extraction removal of light fractions is insufficient. arise.
上記範囲内の割合で、連続的に抽出域に装入された石炭
タールピッチと溶剤は、溶剤の臨界温度〜３７０℃、溶
剤の臨界圧力〜１００ｋｇ／ｃｊＧの圧力に保持され、
軽質留分の抽出除去を行う。Coal tar pitch and solvent are continuously charged into the extraction zone at a ratio within the above range, and are maintained at a critical temperature of the solvent to 370°C and a critical pressure of the solvent to 100 kg/cjG,
The light fraction is extracted and removed.
軽質分の除去率は、得られるバインダーピッチの目標軟
化点により決定されるものであり、高軟化点バインダー
ピッチの製造の場合は除去率を高く、低軟化点バインダ
ーピッチの製造の場合は除去率を低くする。The removal rate of light components is determined by the target softening point of the resulting binder pitch; the removal rate is set high when producing a high softening point binder pitch, and the removal rate is set high when producing a low softening point binder pitch. lower.
軟化点の調整は、溶剤種、溶剤の混合割合、抽出温度及
び圧力により行う。つまり、溶剤は、低軟化点バインダ
ーピッチとする場合はパラフィン系炭化水素溶剤を用い
、高軟化点バインダーピッチとする場合は芳香族系炭化
水素溶剤を用いる。The softening point is adjusted by the solvent type, solvent mixing ratio, extraction temperature, and pressure. That is, as for the solvent, a paraffinic hydrocarbon solvent is used when a low softening point binder pitch is used, and an aromatic hydrocarbon solvent is used when a high softening point binder pitch is used.
パラフィン系炭化水素溶剤を用いた場合に、高軟化点と
するためには溶剤の混合割合を大きくし、低軟化点とす
るためには小さくする。また、芳香族系炭化水素溶剤を
用いた場合は、高軟化点とするためには溶剤の混合割合
を小さくし、低軟化点とするためには大きくする。抽出
域における条件は、高温、低圧で低軟化点、低温、高圧
で高軟化点のピッチが得られる。以上の操作を行うこと
により、軟化点の制御を任意に行うことができる。When a paraffinic hydrocarbon solvent is used, the mixing ratio of the solvent is increased in order to obtain a high softening point, and is reduced in order to obtain a low softening point. In addition, when an aromatic hydrocarbon solvent is used, the mixing ratio of the solvent is decreased in order to obtain a high softening point, and increased in order to obtain a low softening point. The conditions in the extraction zone are high temperature and low pressure to obtain pitch with a low softening point, and low temperature and high pressure to obtain pitch with a high softening point. By performing the above operations, the softening point can be controlled as desired.
抽出除去された軽質留分と抽残骨は抽出域がら連続的に
抜き出される。抽出域から抜き出された軽質留分は常法
に従い溶剤を除去し、溶剤は再使用される。抽残骨はそ
のまま炭素材用バインダーピッチとして使用できる。The extracted light fraction and raffinate bone are continuously extracted from the extraction zone. The light fraction extracted from the extraction zone is stripped of its solvent in a conventional manner and the solvent is reused. The raffle bones can be used as is as a binder pitch for carbon materials.
本発明は、石炭タールピッチが反応しない温度領域での
操作でありメソフェースの生成はない。The present invention operates in a temperature range where coal tar pitch does not react, and no mesophase is generated.
また純溶剤を超臨界状態で使用することにより軽質留分
がシャープに抽出除去されるため、ある−定の軟化点に
調整する場合、軽質留分の混入による軟化点降下を生ず
ることなくより多量の固定炭素成分やβレジン成分を含
有させることができる。In addition, by using a pure solvent in a supercritical state, light fractions are sharply extracted and removed, so when adjusting the softening point to a certain level, a large amount can be used without lowering the softening point due to contamination of light fractions. The fixed carbon component and β resin component can be contained.
これに対して、従来の熱改質反応、あるいは化学反応を
利用する場合は、原１石炭タールピッチが全体的に重質
化すると考えられ、上記軟化点に調整するときには軽質
留分の存在あるいは添加が必要となり、結果的に、固定
炭素やβレジン成分量が低下するものと推定される。On the other hand, when conventional thermal reforming reactions or chemical reactions are used, the raw coal tar pitch is considered to become heavier overall, and when adjusting to the above softening point, the presence of light fractions or It is estimated that addition is necessary, and as a result, the amount of fixed carbon and β-resin components decreases.
以下、実施例にＷづいて本発明方法を具体的に説明する
。Hereinafter, the method of the present invention will be specifically explained based on Examples.
本発明はこの実施例によって限定されるものではない。The invention is not limited to this example.
（実施例−１）
製鉄用コークスを製造する際に副生じたコールタールを
蒸留して得られた石炭タールピッチとしてキノリン不溶
分２．３重ｆｇ％を含有する軟ピツチ（軟化点４０℃）
を使用し、また抽出溶剤としてヘキサンを使用し、第１
図に示すフローシートに従って上記軟ピツチから軽質留
分を抽出除去し炭素材用バインダーピッチを製造した。(Example-1) Soft pitch (softening point 40°C) containing 2.3 weight % of quinoline insoluble content as coal tar pitch obtained by distilling coal tar produced as a by-product during the production of coke for steel making
and using hexane as the extraction solvent, the first
According to the flow sheet shown in the figure, the light fraction was extracted and removed from the soft pitch to produce a binder pitch for carbon materials.
１２０℃に予熱した軟ピツチ１をピッチ供給ポンプ２に
より圧送し、またへキサン３については常温のまま溶剤
供給ポンプ４によりヘキサン／軟ピツチのｍｍ比が１．
２５で圧送し、両者を混合器５で混合し、この軟ピツチ
とへキサンの混合物６を加熱器７で２５５℃に加熱し、
次いでこの混合物を抽出塔８に送入し、２５５℃及び６
０ｋｇ／ｃｄ Ｇの圧力に維持して塔ｍから軽質成分と
溶剤の混合物である抽＋（１相９を連続的に抜出した。The soft pitch 1 preheated to 120°C is pumped by the pitch supply pump 2, and the hexane 3 is fed at room temperature by the solvent supply pump 4 so that the hexane/soft pitch mm ratio is 1.
25, mix the two in a mixer 5, and heat the mixture 6 of soft pitch and hexane to 255°C in a heater 7.
This mixture was then sent to extraction column 8 and heated to 255°C and 6°C.
The extraction phase 9, a mixture of light components and solvent, was continuously withdrawn from column m while maintaining the pressure at 0 kg/cd G.
また塔底からは軽質成分が抽出除去された抽出残渣用１
０を連続的に抜き出し炭素材用バインダーピッチを得た
。塔ｎから抜き出された抽出相９については減圧弁１１
を介して分ＭＷ１２でフラッシュして軽質留分ピッチ１
４、及びヘキサン１３に分離し、ヘキサンは溶剤３とし
て再使用した。In addition, from the bottom of the column, light components are extracted and removed.
0 was continuously extracted to obtain a binder pitch for carbon materials. Pressure reducing valve 11 for extraction phase 9 withdrawn from column n
Light distillate pitch 1 by flashing at min MW 12 through
4 and hexane 13, and hexane was reused as solvent 3.
得られた炭素材用バインダーピッチの性状を第１表−実
施例−１欄に示す。The properties of the obtained binder pitch for carbon materials are shown in Table 1-Example-1 column.
（実施例−２）
実施例−１においてへキサン／軟ピツチの重量比を３．
０に変更し、同様の操作を行った。(Example-2) In Example-1, the weight ratio of hexane/soft pitch was 3.
The value was changed to 0 and the same operation was performed.
得られた炭素月相バインダーピッチの性状を第１表−実
施例−２欄に示す。The properties of the obtained carbon phase binder pitch are shown in Table 1-Example-2 column.
（実施例−３）
実施例−１において抽出溶剤にトルエン、トルエン／軟
ピツチの重量比４．０、抽出温度３４０℃、抽出圧力５
０ｋｇ／ｃ−Ｇに変更し、同様の操作を行った。(Example-3) In Example-1, toluene was used as the extraction solvent, the weight ratio of toluene/soft pitch was 4.0, the extraction temperature was 340°C, and the extraction pressure was 5.
The weight was changed to 0 kg/c-G and the same operation was performed.
得られた炭素材用バインダーピッチの性状を第１表−実
施例−３欄に示す。The properties of the obtained binder pitch for carbon materials are shown in Table 1-Example-3 column.
（比較例−１）
石炭タールピッチとしてあらかじめキノリン不溶分量を
５．９４％に調整した軟ピ・ソチ（軟化点３０℃）を使
用し、低温熱重合反応による熱改質と減圧蒸留による軟
化点調整を行い、炭素材用バインダーピッチを製造した
。(Comparative Example-1) Soft Pisochi (softening point: 30°C) whose quinoline insoluble content was adjusted to 5.94% was used as coal tar pitch, and the softening point was determined by thermal modification by low-temperature thermal polymerization reaction and vacuum distillation. After making adjustments, a binder pitch for carbon material was manufactured.
軟ピツチは重合反応槽において、メンフェースが発生し
ない反応温度３６０℃において１２時間低温熱重合反応
を行い、固定炭素及びβレジンの増加を行った。次いで
減圧蒸留操作により軟化点を８８℃に調整を行い炭素材
用バインダーピ・ソチを得た。The soft pitch was subjected to a low-temperature thermal polymerization reaction for 12 hours at a reaction temperature of 360° C., at which no membranes were generated, in a polymerization reaction tank to increase fixed carbon and β-resin. Next, the softening point was adjusted to 88° C. by distillation under reduced pressure to obtain a binder for carbon materials.
得られた炭素材用バインダーピッチの性状を第２表に示
す。The properties of the obtained binder pitch for carbon materials are shown in Table 2.
第
２
表
比較例１においては長時間、メソフェースの発生し難い
温度に制御するという煩雑な作業が必要にもかかわらず
、本発明により製造した同一軟化点のバインダーピッチ
と比較し、ＦＣ，βレジン含有量とも同等である。In Comparative Example 1 of Table 2, despite the complicated work of controlling the temperature to a temperature that does not easily generate mesophase for a long time, compared with the binder pitch of the same softening point manufactured by the present invention, FC, β resin The content is also the same.
石炭タールピッチを、パラフィン系炭化水素溶剤、また
は芳香族系炭化水素溶剤を用いて、溶剤の超臨界状態に
おいて抽出操作を行い、軽質留分を除去することにより
、複雑な製造工程や多量の副資材を使用することなく、
極めてシンプルかつ安価な方法で、固定炭素が高く、β
レジン含有量が高く、かつメソフェースの発生がない、
炭素材用バインダーピッチを製造することができる。Coal tar pitch is extracted using paraffinic hydrocarbon solvents or aromatic hydrocarbon solvents in the supercritical state of the solvent to remove light fractions, thereby eliminating complex production processes and large amounts of by-products. without using materials,
An extremely simple and inexpensive method with high fixed carbon and β
High resin content and no mesophase generation.
Binder pitch for carbon materials can be manufactured.
第１図は本発明を実施例するためのフローシートの例を
示す図である。
１・・・原料ピッチ、２・・・ピッチ供給ポンプ、３・
・溶剤、４・・・溶剤供給ポンプ、５・・・混合器、６
・・・原料ピッチと溶剤の混合物、７・・・加熱器、８
・・・抽出塔、９・・・抽出相、１０・・・抽出残渣用
、１１・・・減圧弁、１２・・・分離器、１３・・・回
収溶剤、１４・・・軽質留分ピッチ。FIG. 1 is a diagram showing an example of a flow sheet for implementing the present invention. 1... Raw material pitch, 2... Pitch supply pump, 3...
・Solvent, 4... Solvent supply pump, 5... Mixer, 6
...mixture of raw pitch and solvent, 7...heater, 8
...Extraction column, 9.Extraction phase, 10.For extraction residue, 11.Reduction valve, 12.Separator, 13.Recovery solvent, 14.Light fraction pitch. .
Claims (1)
は芳香族系炭化水素溶剤を抽出域に装入し、溶剤の臨界
温度〜３７０℃の温度、溶剤の臨界圧力〜１００ｋｇ／
ｃｍ＾２Ｇの圧力及び溶剤／石炭タールピッチの重量比
０．５〜６．０の範囲の条件下に保持し、石炭タールピ
ッチ中の軽質留分を抽出除去して軟化点８０〜２００℃
となるように調整することを特徴とする炭素材用バイン
ダーピッチの製造方法。 ２、石炭タールピッチが石炭乾留時に副生するコールタ
ールを蒸留して得られる軟化点７０℃以下、キノリン不
溶分（Ｑ１）０．５〜７．０重量％のピッチである請求
項１記載の炭素材用バインダーピッチの製造方法。 ３、パラフィン系炭化水素溶剤、芳香族系溶剤が臨界温
度３６０℃以下、沸点２００℃以下の溶剤である請求項
１記載の炭素材用バインダーピッチの製造方法。[Claims] 1. Coal tar pitch and a paraffinic hydrocarbon solvent or an aromatic hydrocarbon solvent are charged into an extraction zone, and the temperature is from the critical temperature of the solvent to 370°C, and the critical pressure of the solvent is ~100 kg/
The light fraction in the coal tar pitch is extracted and removed under the conditions of a pressure of cm^2G and a weight ratio of solvent/coal tar pitch of 0.5 to 6.0, resulting in a softening point of 80 to 200°C.
A method for producing a binder pitch for carbon materials, which comprises adjusting the pitch so that 2. The coal tar pitch according to claim 1, which is obtained by distilling coal tar produced as a by-product during coal carbonization, has a softening point of 70°C or less, and has a quinoline insoluble content (Q1) of 0.5 to 7.0% by weight. A method for producing binder pitch for carbon materials. 3. The method for producing binder pitch for carbon materials according to claim 1, wherein the paraffinic hydrocarbon solvent and the aromatic solvent have a critical temperature of 360°C or lower and a boiling point of 200°C or lower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7559590A JPH03277690A (en) | 1990-03-27 | 1990-03-27 | Preparation of binder pitch for use in carbon materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7559590A JPH03277690A (en) | 1990-03-27 | 1990-03-27 | Preparation of binder pitch for use in carbon materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03277690A true JPH03277690A (en) | 1991-12-09 |
Family
ID=13580713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7559590A Pending JPH03277690A (en) | 1990-03-27 | 1990-03-27 | Preparation of binder pitch for use in carbon materials |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03277690A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007327033A (en) * | 2006-05-10 | 2007-12-20 | Jfe Chemical Corp | Binder pitch and process for its production |
| JP2013237747A (en) * | 2012-05-14 | 2013-11-28 | Jfe Chemical Corp | Binder pitch and method for producing the same |
| JP2017218486A (en) * | 2016-06-06 | 2017-12-14 | Ｊｆｅケミカル株式会社 | Binder pitch and manufacturing method therefor |
| RU2671354C1 (en) * | 2017-11-20 | 2018-10-30 | Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" | Method for producing a binder pitch with a reduced content of benzopyrene |
-
1990
- 1990-03-27 JP JP7559590A patent/JPH03277690A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007327033A (en) * | 2006-05-10 | 2007-12-20 | Jfe Chemical Corp | Binder pitch and process for its production |
| JP2013237747A (en) * | 2012-05-14 | 2013-11-28 | Jfe Chemical Corp | Binder pitch and method for producing the same |
| JP2017218486A (en) * | 2016-06-06 | 2017-12-14 | Ｊｆｅケミカル株式会社 | Binder pitch and manufacturing method therefor |
| RU2671354C1 (en) * | 2017-11-20 | 2018-10-30 | Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" | Method for producing a binder pitch with a reduced content of benzopyrene |
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