JP2529167B2 - Method for manufacturing pitch for carbon material - Google Patents
Method for manufacturing pitch for carbon materialInfo
- Publication number
- JP2529167B2 JP2529167B2 JP62179217A JP17921787A JP2529167B2 JP 2529167 B2 JP2529167 B2 JP 2529167B2 JP 62179217 A JP62179217 A JP 62179217A JP 17921787 A JP17921787 A JP 17921787A JP 2529167 B2 JP2529167 B2 JP 2529167B2
- Authority
- JP
- Japan
- Prior art keywords
- pitch
- pressure
- carbon material
- molecular weight
- heat 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 - Lifetime
Links
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は炭素材、特に炭素繊維の製造に適した特定の
性状を有する炭素材用ピッチを効率よく製造する方法に
関する。TECHNICAL FIELD The present invention relates to a method for efficiently producing a carbon material, particularly a carbon material pitch having specific properties suitable for producing carbon fibers.
炭素材を得る方法としては近年、石油系の炭素材用ピ
ッチの原料とする方法が多く用いられている。この石油
系の炭素材用ピッチを製造する方法の１つに、不活性ガ
ス吹込み下または減圧下で熱処理する方法があるが、こ
の方法では炭素材用ピッチの収率が低いうえに、熱処理
時間が長いと炭素材用ピッチの流動性も悪くなるため、
炭素繊維の製造に用いると紡糸性が悪くなる等の問題が
あった。As a method for obtaining a carbon material, a method of using a petroleum-based carbon material pitch as a raw material has been widely used in recent years. One of the methods for producing the petroleum-based pitch for carbon material is a method of heat treatment under blowing an inert gas or under reduced pressure. In this method, the yield of the pitch for carbon material is low and the heat treatment is performed. If the time is long, the fluidity of the carbon material pitch will deteriorate,
When used in the production of carbon fibers, there are problems such as poor spinnability.
そこで本発明者らは、上記問題点を解消した炭素材用
ピッチの製造方法を開発すべく鋭意研究を重ねた結果、
特定の性状を有する原料ピッチを用いて加圧下熱処理を
し、次いで減圧下熱処理すれば炭素材用ピッチの収率が
向上し、紡糸性の良好な炭素材用ピッチが得られること
を見出し、本発明に到達した。Therefore, the present inventors have conducted extensive research to develop a method for manufacturing a carbon material pitch that solves the above problems, and as a result,
It was found that a heat treatment under pressure using a raw material pitch having specific properties, and then a heat treatment under reduced pressure improves the yield of the carbon material pitch, and that a carbon material pitch having good spinnability can be obtained. The invention was reached.
すなわち本発明は、石油系重質油中の軽質油分を除去
して得られる、20℃における比重が1.0〜1.35,トルエン
可溶成分の含有量が70％以上，数平均分子量が105〜65
0,全縮合環数が２〜14,ナフテン環数が０〜5,芳香族炭
素分率が0.5〜0.9である原料ピッチを、圧力１〜100kg/
cm2，温度400〜500℃で加圧下熱処理し、次いで圧力0.1
〜50Torr,温度400〜500℃で減圧下熱処理することを特
徴とする炭素材用ピッチの製造方法を提供するものであ
る。That is, the present invention is obtained by removing the light oil component from the petroleum heavy oil, the specific gravity at 20 ℃ is 1.0 to 1.35, the content of toluene soluble components is 70% or more, the number average molecular weight is 105 to 65
0, total condensed ring number 2-14, naphthene ring number 0-5, aromatic carbon fraction 0.5-0.9, the raw material pitch, pressure 1-100kg /
Heat treatment under pressure at cm 2 and temperature 400-500 ℃, then pressure 0.1
The present invention provides a method for manufacturing a pitch for carbon material, which is characterized by performing a heat treatment under reduced pressure at a temperature of 400 to 500 ° C at -50 Torr.
本発明に用いる原料ピッチは、石油類の接触分解残渣
油，熱分解残渣油，水素化分解残渣油などの石油系重質
油から軽質油分を除去したもので、かつ20℃における比
重が1.0〜1.35、好ましくは1.05〜1.35、トルエン可溶
成分の含有量が70％以上、好ましくは90％以上、数平均
分子量（Mn）が105〜650,全縮合環数が２〜14,ナフテン
環数が０〜5,芳香族炭素分率が0.5〜0.9という性状を持
つものである。中でも石油類の接触分解残渣油から得ら
れる上記性状を有する原料ピッチを用いることが好まし
い。なお、全縮合環数およびナフテン環数はWilliams法
（P.B.Williams,Symposium on Composition of Petrole
um Oils,ASTM Special Technical Publication,No.224,
168（1957））および片山法（片山優久雄，石油誌，21,
175（1978））によって求めた値である。また、芳香族
炭素分率とは、芳香族環の骨格を構成する炭素数を原料
ピッチ中の全炭素数で割ったものをいう。軽質油分を除
去するには、上記石油系重質油を予め減圧蒸留して、沸
点約400℃以下（常圧換算）の軽質油分を留去すればよ
い。The raw material pitch used in the present invention is obtained by removing light oil from petroleum heavy oil such as catalytic cracking residual oil of petroleum, thermal cracking residual oil, and hydrocracking residual oil, and has a specific gravity of 1.0 to 20 ° C at 20 ° C. 1.35, preferably 1.05 to 1.35, the content of the toluene-soluble component is 70% or more, preferably 90% or more, the number average molecular weight (Mn) is 105 to 650, the total condensed ring number is 2 to 14, the naphthene ring number is It has a property of 0 to 5 and an aromatic carbon content of 0.5 to 0.9. Above all, it is preferable to use the raw material pitch obtained from the oil of catalytic cracking of petroleum having the above properties. The total condensed ring number and the naphthene ring number are determined by the Williams method (PBWilliams, Symposium on Composition of Petrole
um Oils, ASTM Special Technical Publication, No.224,
168 (1957)) and Katayama method (Yasuo Katayama, Petroleum magazine, 21 ,
175 (1978)). The aromatic carbon fraction means the number of carbon atoms constituting the skeleton of the aromatic ring divided by the total number of carbon atoms in the raw material pitch. In order to remove the light oil component, the above petroleum heavy oil may be distilled under reduced pressure in advance to distill off the light oil component having a boiling point of about 400 ° C. or less (at atmospheric pressure).
なお、本発明において原料ピッチは上記性状の１つで
も欠いていると、炭素材用ピッチの収率が低くなった
り、炭素材を製造しても強度が低くなる等の問題を生じ
るので、上記性状を全て具備していることが必要であ
る。In the present invention, if the raw material pitch lacks even one of the above properties, problems such as low yield of the carbon material pitch and low strength even when the carbon material is manufactured occur. It is necessary to have all the properties.
本発明では、まず上記原料ピッチを圧力１〜100kg/cm
2、好ましくは２〜30kg/cm2，温度400〜500℃、好まし
くは420〜480℃の条件下で通常は0.5〜５時間熱処理を
行なう。なお、不活性ガスによる加圧も可能である。こ
こで圧力が1kg/cm2未満であると、収率が悪いので好ま
しくなく、100kg/cm2を超えると、製造価格の上昇要因
となるので好ましくない。また、温度400℃未満である
と、反応が不充分であるので好ましくなく、500℃を超
えると、製造価格の上昇要因およびコーキング原因とな
るので好ましくない。In the present invention, the raw material pitch is first set to a pressure of 1 to 100 kg / cm.
2 , heat treatment is usually performed for 0.5 to 5 hours under the conditions of 2 to 30 kg / cm 2 , and temperature of 400 to 500 ° C., preferably 420 to 480 ° C. Pressurization with an inert gas is also possible. If the pressure is less than 1 kg / cm 2 , the yield is poor, which is not preferable, and if the pressure exceeds 100 kg / cm 2 , the manufacturing cost is increased, which is not preferable. On the other hand, if the temperature is lower than 400 ° C, the reaction is insufficient so that it is not preferable.
加圧下熱処理した原料ピッチを減圧下熱処理するに先
立って、好ましくは該ピッチをフラッシュドラムなどの
装置に導き、低分子量成分を除去する。除去した低分子
量成分は、原料ピッチとして加圧熱処理の工程に戻して
再利用することができる。低分子量成分を原料ピッチと
して再利用すると、次第に低分子量成分が結合し高分子
量成分となり、炭素材用ピッチが形成されるなど、炭素
材用ピッチの収率を向上させることになり好ましい。Prior to heat-treating the material pitch heat-treated under pressure under reduced pressure, the pitch is preferably introduced into a device such as a flash drum to remove low molecular weight components. The removed low molecular weight component can be reused as a raw material pitch by returning it to the process of pressure heat treatment. When the low molecular weight component is reused as the raw material pitch, the low molecular weight component is gradually combined to become a high molecular weight component, and the carbon material pitch is formed, which is preferable because the yield of the carbon material pitch is improved.
次に、上記原料ピッチを減圧下熱処理する。まず、該
原料ピッチを薄膜蒸発器などの反応器に導入し、圧入0.
1〜50Torr、好ましくは0.5〜5Torr,温度400〜500℃、好
ましくは430〜480℃の条件で通常は10分〜２時間、減圧
下で熱処理を行なう。ここで圧力が0.1Torr未満である
と、収率が低下するので好ましくなく、50Torrを超える
と、メソ相への転化が不充分であるので好ましくない。
また、温度が400℃未満では、反応が不充分であるので
好ましくなく、500℃を超えると、炭化が進みすぎコー
キングの原因となるので好ましくない。減圧下で熱処理
する際に低分子量成分を除去することが望ましく、除去
した低分子量成分は前記と同様に、炭素材用ピッチの収
量を向上させる目的で原料ピッチとして再利用するため
に加圧下熱処理工程に戻すことができる。Next, the raw material pitch is heat-treated under reduced pressure. First, the raw material pitch was introduced into a reactor such as a thin film evaporator, and press-fitting was performed.
Heat treatment is carried out under reduced pressure for 1 to 50 Torr, preferably 0.5 to 5 Torr, temperature of 400 to 500 ° C., preferably 430 to 480 ° C., usually for 10 minutes to 2 hours. If the pressure is less than 0.1 Torr, the yield is lowered, which is not preferable, and if it exceeds 50 Torr, the conversion to the meso phase is insufficient, which is not preferable.
On the other hand, if the temperature is lower than 400 ° C, the reaction is insufficient and therefore it is not preferable. It is desirable to remove low molecular weight components during heat treatment under reduced pressure, and the removed low molecular weight components are heat treated under pressure in order to reuse as raw material pitch for the purpose of improving the yield of pitch for carbon material, as described above. Can be returned to the process.
本発明の方法にしたがえば、重量平均分子量（Mw）と
数平均分子量（Mn）の比、Mw/Mn＝1.1〜2.5、好ましく
は1.5〜1.7,数平均分子量が700〜1500、好ましくは800
〜1200,キノリン不溶分（QI）の含有量が５〜60重量
％、好ましくは10〜30重量％，メソ相含有量30〜100重
量％、好ましくは60〜100重量％，分子量3000以上の分
率が20％以下、好ましくは３〜５％，軟化点が260〜380
℃である炭素材用ピッチが効率よく製造できる。According to the method of the present invention, the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn), Mw / Mn = 1.1 to 2.5, preferably 1.5 to 1.7, the number average molecular weight is 700 to 1500, preferably 800.
Content of quinoline insoluble matter (QI) is 5 to 60% by weight, preferably 10 to 30% by weight, mesophase content of 30 to 100% by weight, preferably 60 to 100% by weight, and molecular weight of 3000 or more. The ratio is 20% or less, preferably 3 to 5%, and the softening point is 260 to 380.
It is possible to efficiently manufacture a carbon material pitch that is ℃.
このようにして得られた炭素材用ピッチは各種炭素製
品の製造に供給され、たとえばピッチ系炭素繊維を製造
するには、常法によりまずこのピッチを紡糸し、次いで
不融化処理し、さらに焼成すればよく、得られた炭素繊
維は機械的強度が高いものである。The pitch for carbon material thus obtained is supplied to the production of various carbon products. For example, in order to produce pitch-based carbon fiber, this pitch is first spun by a conventional method, then infusibilized, and further fired. The carbon fiber obtained has high mechanical strength.
次に、本発明を実施例により説明する。 Next, the present invention will be described with reference to examples.
実施例１ デカントオイルの軽質留分を80％除去したピッチ（比
重1.12,トルエン可溶成分78重量％，数平均分子量510,
全縮合環数8,ナフテン環数0.8,芳香族炭素分率0.82）を
原料ピッチとし、この原料ピッチ1kgをオートクレーブ
に入れ、窒素初期圧5kg/cm2Ｇで攪拌しながら450℃で30
分間加熱処理を行なった。次いで、1Torr,450℃で30分
間、400rpmで攪拌しながら減圧熱処理を行なった。得ら
れた炭素材用ピッチの性状を第１表に示す。Example 1 Pitch from which 80% of the light fraction of decant oil was removed (specific gravity 1.12, toluene soluble component 78% by weight, number average molecular weight 510,
Total condensed ring number 8, naphthene ring number 0.8, aromatic carbon fraction 0.82) was used as the raw material pitch, and 1 kg of this raw material pitch was put into an autoclave, and the initial nitrogen pressure was 5 kg / cm 2 G while stirring at 450 ℃ 30
Heat treatment was performed for a minute. Then, reduced pressure heat treatment was performed at 1 Torr and 450 ° C. for 30 minutes while stirring at 400 rpm. Table 1 shows the properties of the obtained pitch for carbon material.
得られた炭素材用ピッチを押出機により、穴径0.3mm,
長さ1.2mmのキャピラリーを通し、剪断速度400sec-1で
押出し、500m/minの速度で巻き取ったところ、５分以上
糸が切れなかった。この繊維を300℃で30分間不融化処
理した後、1500℃で焼成した。得られた炭素繊維の強度
および弾性率を第１表に示す。The obtained carbon material pitch with an extruder, hole diameter 0.3mm,
When it was extruded at a shear rate of 400 sec -1 through a capillary having a length of 1.2 mm and wound at a speed of 500 m / min, the yarn was not broken for more than 5 minutes. This fiber was infusibilized at 300 ° C. for 30 minutes and then fired at 1500 ° C. Table 1 shows the strength and elastic modulus of the obtained carbon fiber.
比較例１ 実施例１において、加圧熱処理を行なわなかったこと
以外は実施例１と同様の操作を行ない、炭素材用ピッチ
を得た。得られた炭素材用ピッチの性状を第１表に示
す。Comparative Example 1 The same operation as in Example 1 was carried out except that pressure heat treatment was not performed in Example 1, to obtain a carbon material pitch. Table 1 shows the properties of the obtained pitch for carbon material.
この炭素材用ピッチを実施例１と同様の操作により紡
糸したところ、５分以内で糸が切れた。さらに、実施例
１と同様の操作により不融化および焼成をし、炭素繊維
を得た。得られた炭素繊維の性状を第１表に示す。When this carbon material pitch was spun in the same manner as in Example 1, the yarn was broken within 5 minutes. Further, infusibilization and firing were carried out in the same manner as in Example 1 to obtain carbon fibers. The properties of the obtained carbon fiber are shown in Table 1.
実施例２ 実施例１で用いた原料ピッチ1kgをオートクレーブに
入れ、20kg/cm2で攪拌しながら450℃で平均滞留時間30
分で加圧熱処理し、次いでフラッシュドラムに導き、低
分子量成分を除去した。除去した低分子量成分は原料ピ
ッチとして加圧熱処理工程に戻して再利用した。次い
で、低分子量成分を除去したピッチをギヤーポンプによ
り薄膜蒸発器に導入し、窒素ガス流通下で1Torr,450℃
で平均滞留時間12分で減圧熱処理を行なった。なお、薄
膜蒸発器は回転複数羽根を有するものを用いた。減圧処
理時に除去された低分子量成分も原料ピッチとして加圧
熱処理工程に戻し、再利用した。得られた炭素材用ピッ
チの性状を第１表に示す。Example 2 1 kg of the raw material pitch used in Example 1 was placed in an autoclave and stirred at 20 kg / cm 2 at 450 ° C. for an average residence time of 30.
Pressure heat treated in minutes and then led to a flash drum to remove low molecular weight components. The removed low molecular weight component was reused as the raw material pitch by returning it to the pressure heat treatment step. Then, the pitch from which low molecular weight components were removed was introduced into the thin film evaporator by a gear pump, and 1 Torr, 450 ° C under nitrogen gas flow.
A vacuum heat treatment was performed with an average residence time of 12 minutes. The thin film evaporator used had a plurality of rotating blades. The low molecular weight component removed during the pressure reduction treatment was also returned to the pressure heat treatment step as a raw material pitch and reused. Table 1 shows the properties of the obtained pitch for carbon material.
この炭素材用ピッチを実施例１と同様の操作により紡
糸したところ、５分以上糸が切れなかった。さらに、実
施例１と同様の操作により不融化および焼成をし、炭素
繊維を得た。得られた炭素繊維の性状を第１表に示す。When this carbon material pitch was spun in the same manner as in Example 1, the yarn was not broken for 5 minutes or more. Further, infusibilization and firing were carried out in the same manner as in Example 1 to obtain carbon fibers. The properties of the obtained carbon fiber are shown in Table 1.
比較例２ 実施例２において、加圧熱処理を行わなったこと以外
は実施例２と同様の操作を行ない、炭素材用ピッチを得
た。得られた炭素材用ピッチの性状を第１表に示す。Comparative Example 2 In Example 2, the same operation as in Example 2 was performed except that the pressure heat treatment was performed to obtain a carbon material pitch. Table 1 shows the properties of the obtained pitch for carbon material.
得られた炭素材用ピッチを実施例１と同様の操作によ
り紡糸したところ、５分以内で糸が切れた。さらに、実
施例１と同様に操作により不融化および焼成をし、炭素
繊維を得た。得られた炭素繊維の性状を第１表に示す。When the obtained pitch for carbon material was spun by the same operation as in Example 1, the yarn was broken within 5 minutes. Further, infusibilization and firing were performed by the same procedure as in Example 1 to obtain carbon fibers. The properties of the obtained carbon fiber are shown in Table 1.
〔発明の効果〕 本発明の方法によれば、炭素材用ピッチを効率よく製
造することができるうえ、本発明の炭素材用ピッチから
得られる炭素材は引張強度，弾性率などの性質にすぐれ
ている。したがって、本発明は炭素繊維，ヤーン，フィ
ラメント，リボン，フィルムなどの各種炭素製品の製造
に有用なものである。 [Advantages of the Invention] According to the method of the present invention, the carbon material pitch can be efficiently produced, and the carbon material obtained from the carbon material pitch of the present invention has excellent properties such as tensile strength and elastic modulus. ing. Therefore, the present invention is useful in the production of various carbon products such as carbon fibers, yarns, filaments, ribbons and films.
Claims (2)
れる、20℃における比重が1.0〜1.35,トルエン可溶成分
の含有量が70％以上，数平均分子量が105〜650,全縮合
環数が２〜14,ナフテン環数が０〜5,芳香族炭素分率0.5
〜0.9である原料ピッチを、圧力１〜100kg/cm2，温度40
0〜500℃で加圧下熱処理し、次いで圧力0.1〜50Torr,温
度400〜500℃で減圧下熱処理することを特徴とする炭素
材用ピッチの製造方法。1. A specific gravity at 20 ° C. obtained by removing the light oil component from a petroleum heavy oil, the content of the toluene soluble component is 70% or more, the number average molecular weight is 105 to 650, Total condensed ring number 2-14, naphthene ring number 0-5, aromatic carbon fraction 0.5
Raw material pitch of ~ 0.9, pressure 1 ~ 100kg / cm 2 , temperature 40
A process for producing a pitch for carbon material, which comprises heat-treating under pressure at 0 to 500 ° C, and then heat-treating at pressure 0.1 to 50 Torr and temperature 400 to 500 ° C under reduced pressure.
において低分子量成分を除去し、該低分子量成分を該加
圧下熱処理工程に原料ピッチとして再利用することを特
徴とする特許請求の範囲第１項記載の製造方法。2. A low molecular weight component is removed in a heat treatment under pressure and a heat treatment under reduced pressure, and the low molecular weight component is reused as a raw material pitch in the heat treatment under pressure. The manufacturing method according to the item.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62179217A JP2529167B2 (en) | 1987-07-20 | 1987-07-20 | Method for manufacturing pitch for carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62179217A JP2529167B2 (en) | 1987-07-20 | 1987-07-20 | Method for manufacturing pitch for carbon material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6424889A JPS6424889A (en) | 1989-01-26 |
| JP2529167B2 true JP2529167B2 (en) | 1996-08-28 |
Family
ID=16061984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62179217A Expired - Lifetime JP2529167B2 (en) | 1987-07-20 | 1987-07-20 | Method for manufacturing pitch for carbon material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2529167B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20230037591A (en) * | 2020-07-13 | 2023-03-16 | 토마스 씨 홀컴 | Pitch process and product |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6232179A (en) * | 1985-08-01 | 1987-02-12 | Koa Sekiyu Kk | Preparation of raw material pitch for carbonaceous material |
-
1987
- 1987-07-20 JP JP62179217A patent/JP2529167B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6232179A (en) * | 1985-08-01 | 1987-02-12 | Koa Sekiyu Kk | Preparation of raw material pitch for carbonaceous material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6424889A (en) | 1989-01-26 |
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