JPH0730338B2 - Continuous production method of precursor for high strength and high elasticity carbon fiber - Google Patents

Description

【発明の詳細な説明】 〔産業上の利用分野〕 脱硫減圧軽油の熱接触分解（FCC）に依つて副生する石
油系ピツチを造る原料の原油の種類は多種多様でその組
成、成分も複雑でこれ等の影響を極力抑制し、更らに石
油系ピツチ中に混入するQ.i.成分（リチユムで水添して
も溶剤に不溶）及び無機質物を除去した高強度超高弾性
炭素繊維製造用の前駆体の製法に関する。[Detailed Description of the Invention] [Industrial field of application] There are various types of crude oil as a raw material for the production of petroleum-based pitch, which is a by-product of thermal catalytic cracking (FCC) of desulfurized vacuum gas oil, and its composition and composition are complicated. In order to suppress these effects as much as possible, and to remove the Qi component (insoluble in the solvent even if hydrogenated with lithium) and the inorganic substances that are further mixed in the petroleum-based pitch, for the production of high-strength ultra-high elastic carbon fiber It relates to a method for producing a precursor.

〔従来の技術〕[Conventional technology]

近年航空機、自動車、その他の輸送機製作工業の急速な
成長の結果、物理性質がユニークで且つ特別な物質との
組合わせに依つて極めて勝れた特性を発揮する材料を望
む声が大きくクローズアツプされ、この要望に答えるた
めの研究が複合材（強化樹脂）の製造に集中している。As a result of the rapid growth of the aircraft, automobile and other transportation equipment manufacturing industries in recent years, there is a great demand for materials that have unique physical properties and that exhibit extremely superior properties depending on the combination with special materials. Therefore, research to meet this demand is concentrated on the production of composite materials (reinforced resin).

強化樹脂に使用される最も有望な材料の一つとして高強
度高弾性炭素繊維がある。この材料は前述の産業の急速
な成長が起りつゝある際に現われて来たもので、この炭
素繊維と樹脂と組合わせて使用すると、他に全くその例
を見ないような特性を発揮する強化樹脂を製造すること
が出来る。現在入手出来る高強度高弾性炭素繊維の原料
は特殊な製造法及び紡糸性に依つて製糸されるアクリロ
ニトリル繊維が主であることは公知の事実であるが、ア
クリロニトリル繊維より造るPAN系炭素繊維は高価であ
るばかりでなく、複合材のフイラーとしては弾性が不充
分で、より高弾性炭素繊維が強く要求されている。One of the most promising materials used for reinforcing resin is high strength and high elasticity carbon fiber. This material has emerged during the rapid growth of the industry mentioned above, and when used in combination with this carbon fiber and resin, it exhibits properties that are unprecedented. A reinforced resin can be manufactured. It is a known fact that currently available raw materials for high-strength and high-elasticity carbon fibers are acrylonitrile fibers that are spun according to a special manufacturing method and spinnability, but PAN-based carbon fibers made from acrylonitrile fibers are expensive. Not only that, but the elasticity of the filler as a composite material is insufficient, and there is a strong demand for higher elastic carbon fibers.

高強度高弾性炭素繊維を安価に製造する方法が特公昭48
−36,160、特公昭48−122,122及び特公昭53−65,425等
その他多くの特許文献に公知されている。即ち石油系ピ
ツチを回分式加熱処理器で温度380℃乃至440℃で加熱時
間30分乃至30時間加熱処理して、メソフエーズ（偏光顕
微鏡で容易に確認することが出来る）を40％乃至約100
％含有するピツチを製造し、この生成ピツチをそのまま
炭素繊維用前駆体として使用しているが、この場合原料
は脱硫減圧軽油の原料の油種に依つて石油系ピツチの成
分及び組成が多種多様であるため、この石油系ピツチを
原料として造る前駆体（メソフエーズを含有するピツ
チ）の組成及び成分は何時も安定しているとは云えな
い。更らに、円筒型の加熱器を用して石油系ピツチを温
度380℃乃至440℃で加熱処理する際、加熱反応器の器壁
にコーキング起り加熱処理を中止せざるを得ない事故が
発生する。これ等石油系ピツチの原料の油種及びメソフ
エーズ生成のための加熱処理時のコーキングの問題は未
だ充分解決されていない。Japanese Patent Publication Sho 48
-36,160, JP-B-48-122,122 and JP-B-53-65,425 and many other patent documents are known. That is, a petroleum-based pitch is heat-treated at a temperature of 380 ° C to 440 ° C for a heating time of 30 minutes to 30 hours in a batch type heat treatment device, and the mesophase (which can be easily confirmed by a polarization microscope) is 40% to about 100%.
% Pitch is produced and this generated pitch is used as it is as a precursor for carbon fiber. In this case, the raw material has a wide variety of petroleum-based components and compositions depending on the type of raw material of desulfurized vacuum gas oil. Therefore, it cannot be said that the composition and components of the precursor (pitch containing mesophase) produced from the petroleum-based pitch as a raw material are always stable. Furthermore, when a petroleum-based pitch is heat-treated at a temperature of 380 ° C to 440 ° C using a cylindrical heater, coking occurs on the wall of the heating reactor, and an accident has to be stopped. To do. The problems of the oil species of these petroleum-based pitches and the coking during the heat treatment for forming the mesophases have not yet been sufficiently solved.

〔発明が解決しようとする問題点〕[Problems to be solved by the invention]

脱硫減圧軽油の熱接触分解（FCC）に依つて造る石油系
ピツチを原料とする炭素繊維製造法で、原料である原油
の油種が極めて多種多様で複雑なため製造工程に色々な
影響を与える。又石油系ピツチを原料として加熱処理す
る場合加熱反応器の器壁にコーキングが起り、加熱処理
を中止することを余儀なくされる。石油系ピツチの原料
の多様性から来る問題点を極力抑制し、更に加熱反応で
起るコーキングを無くする手段を提供することが本発明
の目的である。A carbon fiber manufacturing method that uses petroleum-based pitch as a raw material, which is produced by the thermal catalytic cracking (FCC) of desulfurized vacuum gas oil, and because the crude oil that is the raw material is extremely diverse and complicated, it affects various manufacturing processes. . Further, when heat treatment is performed using petroleum-based pitch as a raw material, coking occurs on the wall of the heating reactor, and it is unavoidable to stop the heat treatment. It is an object of the present invention to provide means for suppressing the problems caused by the diversity of petroleum-based raw materials as much as possible, and further for eliminating the coking caused by the heating reaction.

〔問題を解決する手段〕[Means for solving problems]

上記の目的は本発明の管状加熱器及びそれに対応する加
熱処理方法の採用に依つて解決される。The above object is solved by adopting the tubular heater and the corresponding heat treatment method of the present invention.

本発明は脱硫減圧軽油の熱接触分解（FCC）に依つて副
生される石油系ピツチを減圧蒸留して、80％以上をカツ
トした留分（初留450℃乃至終留560℃）は脱硫減圧軽油
の原料の油種（それは中東原油、アラビヤ原油、クエー
ト原油、マーバン原油、ガツチ原油、その他）に依りそ
の成分組成も常時変化し、このために起る問題及びこの
石油系ピツチを一般の円筒型の加熱処理器で加熱する際
器壁の表面にコーキングが発生して加熱処理を中止する
ことが余儀なくされる。これ等の難問題を解決すると同
時に安価で且つ常時安定した物性及び組成を有する高強
度超高弾性炭素繊維製造用の前駆体を製造する方法につ
いて種々研究した結果次の如き管式加熱反応器と反応条
件を採用することでこれらの問題を解決した。次の条件
が本発明の特徴である。即ち １）石油系ピツチを管式加熱処理でメソフエーズを５％
乃至15％生成する条件として加熱温度380℃乃至500℃、
圧力10kg/cm²乃至150kg/cm²、加熱時間30分乃至３時間
を採用する。Desulfurization Desulfurization Petroleum-based pitch, which is a by-product of thermal catalytic cracking (FCC) of vacuum gas oil, is distilled under reduced pressure, and 80% or more of the cut fractions (initial distillation 450 ° C to final distillation 560 ° C) are desulfurized Depending on the type of raw material of vacuum gas oil (that is, Middle East crude oil, Arabia crude oil, Kuwait crude oil, Mavan crude oil, Gutchi crude oil, etc.), its composition is constantly changing, and the problems caused by this change and this petroleum-based pitch When heating with a cylindrical heat treatment device, coking occurs on the surface of the vessel wall, and the heat treatment must be stopped. As a result of various researches on the method for producing the precursor for producing the high-strength ultrahigh-elastic carbon fiber which is inexpensive and always has stable physical properties and composition at the same time as solving these difficult problems, the results of various studies are shown as follows. These problems were solved by adopting the conditions. The following conditions are the features of the present invention. That is, 1) Petroleum-based pitch is treated by pipe heating to obtain 5% mesophase.
Heating temperature of 380 ℃ to 500 ℃,
The pressure is 10 kg / cm ^{2 to} 150 kg / cm ² , and the heating time is 30 minutes to 3 hours.

２）管状の加熱処理器の管径は回分式の円筒形の加熱処
理器の内径の数百分の１で極めて小さいので、極めて粘
度の高い石油系ピツチを加熱する加熱処理器の器壁の温
度と加熱生成ピツチの温度との差は殆ど無い、このた
め、プロトンの発生もより少なく、更らに生成ピツチ内
の温度差も極めて小さいため、生成ピツチの物性及びそ
の組成は管内では全く等しく、更らに非酸化性ガスを反
応管に送入することに依りコーキングの発生も全く無
く、石油系ピツチの原油の油種に依る影響をよく抑制で
きる。又極めて安定で且つ均質の成分及び組成を有する
高強度超高弾性炭素繊維用前駆体を連続的に製造でき
る。2) Since the tube diameter of the tubular heat treatment device is a few hundredth of the inner diameter of the batch-type cylindrical heat treatment device, it is extremely small, so that the wall of the heat treatment device that heats the extremely high-viscosity petroleum-based pitch There is almost no difference between the temperature and the temperature of the heat-produced pitch.Therefore, the generation of protons is smaller and the temperature difference in the generated pitch is also extremely small.Therefore, the physical properties and composition of the generated pitch are exactly the same in the tube. Further, by feeding a non-oxidizing gas into the reaction tube, there is no occurrence of coking, and the effect of the type of crude petroleum pitch crude oil can be well suppressed. Further, it is possible to continuously produce a precursor for high-strength ultrahigh-elasticity carbon fiber having extremely stable and homogeneous components and composition.

３）石油系ピツチの原料の原油の油種の組成及び成分に
依る影響を極力抑制して管形の加熱処理器の出口から常
時全く同じ組成、成分の生成ピツチが流出される。3) The production pitch of the exact same composition and component is always discharged from the outlet of the tubular heat treatment device while suppressing the influence of the composition and component of the crude oil as the raw material of the petroleum-based pitch as much as possible.

４）管式の加熱処理器でメソフエーズを５％乃至15％含
有する様な加熱処理条件で生成ピツチを造り、この生成
ピツチを熟成しメソフエーズのみを熟成融着させその融
着巨大化したメソフエーズ中に石油系ピツチ中に既存す
るQ.i.成分（このQ.i.成分は水添しても溶剤に不溶）及
び無機質物をも包含して、熟成温度でメソフエーズ層と
上層に全くメソフエーズを含有せぬ非メソピツチ（偏光
顕微鏡にて全くメソフエーズの存在は認められぬ）とに
比重の差で画然と分離精製する。この精製される全くメ
ソフエーズを含有せぬ非メソピツチを高強度超高弾性炭
素繊維製造用の前駆体として使用する。4) Using a tubular heat treatment device, make a produced pitch under the heat treatment conditions that contain 5% to 15% of mesophase, and age the produced pitch to age and fuse only the mesophase. In addition to the existing Qi component in the petroleum-based pitch (this Qi component is insoluble in the solvent even when hydrogenated) and the inorganic substance, the mesophase layer and the upper layer do not contain any mesophase at the aging temperature. The presence of mesophases is not observed at all under a polarizing microscope), and the difference in specific gravity significantly separates and purifies. The purified non-mesophase containing no mesophase is used as a precursor for producing a high-strength ultrahigh-elasticity carbon fiber.

脱硫減圧軽油の熱接触分解（FCC）に依つて副生する石
油系ピツチを減圧蒸留して80％乃至85％カツトした留分
（初留450℃乃至460℃終留560℃、H.成分20.0％乃至83.
3％、B.成分16.0％乃至70.0％、Q.i.成分0.2％以下、無
機質物0.1％以下）を前述の本発明の特徴的条件を採用
して生成ピツチを造り、このピツチを温度300℃乃至350
℃で熟成時間５時間乃至40時間かけて熟成してピツチ中
のメソフエーズのみを融着巨大化させ、この巨大化され
たメソフエーズ中に原料の石油系ピツチ中に混入してい
たQ.i.成分（このQ.i.成分はリチユムにて水添しても溶
剤に不溶）及び無機質物を包含しその熟成温度で全くメ
ソフエーズを含有せぬ非メソピツチ（H.成分12.0％乃至
20.0％、B.成分24.0％乃至42.0％、Q.i.成分0.6％以
下、このQ.i.成分は水添に依つて溶剤に可溶、無機質物
無し）と下層に巨大化されたメソフエーズピツチとを比
重の差に依つて画然と分離する処理工程に依つて始めて
石油系ピツチを造る原油の油種に依る影響を極力抑制
し、コーキングの発生もなく、石油系ピツチ中混入する
Q.i.成分（このQ.i.成分はリチユムにて水添しても溶剤
に不溶）及び無機質物の無い高強度高弾性炭素繊維用の
前駆体を製造する。80% to 85% cut fraction of the petroleum-based pitch produced as a by-product of thermal catalytic cracking (FCC) of desulfurized vacuum gas oil (first distillation 450 ° C to 460 ° C final distillation 560 ° C, H. component 20.0%) % To 83.
3%, B. component 16.0% to 70.0%, Qi component 0.2% or less, inorganic substance 0.1% or less) are produced by using the above-mentioned characteristic conditions of the present invention to make a pitch.
After aging at ℃ for 5 to 40 hours, only the mesophases in the pitch are fused and huge, and the Qi component (the Qi Ingredients are non-mesopitches (insoluble in solvent even when hydrogenated with lithium) and inorganic substances and contain no mesophase at the aging temperature (H. component 12.0% to
20.0%, B. component 24.0% to 42.0%, Qi component 0.6% or less, this Qi component is soluble in the solvent due to hydrogenation, there is no inorganic substance) and the specific gravity of the enormous mesophase pitch in the lower layer A petroleum-based pitch is produced only by a treatment process that is distinctly separated according to the difference in oil content. The effect of the type of crude oil is suppressed as much as possible, no coking occurs, and it is mixed in the petroleum-based pitch.
A precursor for a high-strength and high-elasticity carbon fiber having no Qi component (this Qi component is insoluble in a solvent even when hydrogenated with lithium) and an inorganic substance is produced.

本発明方法で使用する非酸化性ガスとしてはエタン、プ
ロパン、ブタン、重質化しない低沸点のナフサ、この加
熱処理で副生するドライガス（その一例を挙げると水素
6.0％、メタン74.0％、エタン13.3％、プロパン3.6％、
ブタン1.3％、ペンタン0.9％、その他0.9％）及び水素
を挙げることが出来る。Examples of the non-oxidizing gas used in the method of the present invention include ethane, propane, butane, naphtha having a low boiling point that does not heavier, and dry gas produced as a by-product of this heat treatment (for example, hydrogen).
6.0%, methane 74.0%, ethane 13.3%, propane 3.6%,
Butane 1.3%, pentane 0.9%, other 0.9%) and hydrogen.

尚非酸化性ガスを使用する場合には原料の石油系ピツチ
kg当り0.05／分乃至1.0／分で充分で極めて少量で
その効果を充分発揮することが出来る。If non-oxidizing gas is used, the petroleum-based
0.05 / min to 1.0 / min is sufficient per kg, and the effect can be sufficiently exerted even with an extremely small amount.

この非メソピツチは物性も優れ、この非メソを原料とし
て100％メソフエーズピツチを製造するとその収率は85
％乃至95％である。This non-meso-pitch has excellent physical properties, and if 100% mesophase pitch is produced from this non-meso as a raw material, the yield is 85%.
% To 95%.

実施例１ 脱硫減圧軽油の熱接触分解（FCC）に依つて副生する石
油系ピツチを減圧蒸留し85％カツトした留分（初留400
℃乃至終留560℃、H.成分82.7％平均分子量382M.P.45℃
乃至46℃、B.成分17.0％M.P.97℃平均分子量450、Q.i.
成分0.2％、無機質物0.1％以下）1,260gr/Hr及びプロパ
ンガス500cc/Hrを共に管の内径4cm、長さ2mの管状の加
熱処理器に圧入し、圧力30kg/cm²加熱温度400℃加熱時
間２時間加熱処理してメソフエーズを10.6％含有する物
性、組成の安定したピツチ692gr/Hrを連続的且つ安定的
に製造することが出来た。この生成ピツチを熟成温度32
0℃、熟成時間20時間でメソフエーズピツチのみを熟成
し、融着巨大化させ、熟成温度320℃で下層にメソフエ
ーズピツチと上層に全くメソフエーズピツチを含有せぬ
非メソピツチ（H.成分15.9％、平均分子量323、M.P.43
℃乃至44℃、B.成分35.4％、平均分子量504、M.P.107
℃、Q.S.成分48.3％、Q.i.成分0.4％、このQ.i.成分は
水添すると可溶で、原料の石油系ピツチに混入していた
Q.i.成分とは全く異なる。無機質物０）とに比重の差で
分離精製して非メソピツチを造り、これを高強度超高弾
性炭素繊維用の前駆体として使用した。Example 1 A fraction obtained by distilling a petroleum-based pitch by-produced by thermal catalytic cracking (FCC) of desulfurized vacuum gas oil to 85% cut (initial distillation 400
℃ to final distillation 560 ℃, H. component 82.7% average molecular weight 382M.P.45 ℃
~ 46 ℃, B. component 17.0% MP97 ℃ Average molecular weight 450, Qi
(Ingredients 0.2%, minerals 0.1% or less) 1,260 gr / Hr and propane gas 500 cc / Hr are pressed into a tubular heat treatment device with an inner diameter of 4 cm and a length of 2 m, and the pressure is 30 kg / cm ² Heating temperature is 400 ° C By heating for 2 hours, Pitch 692 gr / Hr containing 10.6% of mesophase and having stable physical properties and composition could be continuously and stably produced. Aging temperature of this produced pitch is 32
Only the mesophase pitch is matured at 0 ° C for 20 hours, and the fusion is enlarged to a large size. Ingredient 15.9%, average molecular weight 323, MP43
℃ ~ 44 ℃, B. component 35.4%, average molecular weight 504, MP107
℃, QS component 48.3%, Qi component 0.4%, this Qi component was soluble when hydrogenated and was mixed in the petroleum-based pitch as a raw material
It is completely different from the Qi component. Non-mesopitches were produced by separating and purifying the inorganic substances 0) with a difference in specific gravity, and used as precursors for high-strength ultrahigh-elasticity carbon fibers.

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】H.成分：サンプル10gをヘプタン150cc、抽
出温度98.4℃で抽出される成分。 B.成分：前述のH.成分の溶剤抽出に依つて抽出されない
H.不溶分をベンゼン150cc、温度80.1℃で抽出される成
分。 Q.S.成分：前述のB.成分の溶剤抽出に依つて抽出されな
いB.不溶分をキノリン150cc、温度237℃で抽出される成
分。 Q.i.成分：前述のQ.S.成分の溶剤抽出に依つて抽出され
ないQ.S.不溶分として、 脱硫減圧軽油の熱接触分解（FCC）に依つて副生する石
油系ピツチを減圧蒸留して80％乃至85％カツトした留分
（初留450℃乃至460℃、終留560℃、H.成分20.0％乃至8
3.0％、B.成分16.0％乃至70.0％、Q.i.成分0.2％以下、
無機質0.1％以下）を管状加熱反応器に依り温度380℃乃
至500℃で加熱し、非酸化性ガスを管状加熱反応器内に
圧入し、メソフエーズピツチを５％乃至15％含有する生
成物を得、この生成物を温度300℃乃至350℃で熟成処理
し、上層に全くメソフエーズを含有せぬ非メソピツチ
（H.成分12.0％乃至20.0％、B.成分24.0％乃至48.0％、
Q.i.成分0.6％以下、このQ.i.成分は水添に依つて溶剤
に可溶、無機質物無し）を比重の差に依つてメソフエー
ズピツチ層から画然と区分して、分離精製して得ること
を特徴とする高強度超高弾性炭素繊維製造用の前駆体と
しての非メソピツチの製造法。1. H. component: A component extracted from 10 g of a sample at 150 cc of heptane at an extraction temperature of 98.4 ° C. Component B: Not extracted by solvent extraction of component H. mentioned above
H. Insoluble matter is extracted with benzene 150cc at a temperature of 80.1 ℃. QS component: A component that is extracted at 150 cc of quinoline at a temperature of 237 ° C for the B. insoluble matter that is not extracted by the solvent extraction of the aforementioned B. component. Qi component: As a QS insoluble component that is not extracted by solvent extraction of the above-mentioned QS component, a petroleum-based pitch that is a by-product of thermal catalytic cracking (FCC) of desulfurized vacuum gas oil is distilled by vacuum and 80% to 85% cut Fractions (initial distillation 450 ℃ ~ 460 ℃, final distillation 560 ℃, H. component 20.0% ~ 8
3.0%, B. component 16.0% to 70.0%, Qi component 0.2% or less,
Inorganic substance (0.1% or less) is heated at a temperature of 380 to 500 ° C by a tubular heating reactor, a non-oxidizing gas is pressed into the tubular heating reactor, and a product containing 5% to 15% of mesophase pitch. The resulting product is aged at a temperature of 300 ° C. to 350 ° C., non-mesopitches containing no mesophase in the upper layer (H. component 12.0% to 20.0%, B. component 24.0% to 48.0%,
0.6% or less of Qi component, this Qi component is soluble in the solvent due to hydrogenation, no inorganic substances) is distinctly separated from the mesophase pitch layer according to the difference in specific gravity, and separated and purified. A process for producing non-mesopitches as a precursor for producing high-strength ultrahigh-elasticity carbon fibers, characterized by: 【請求項２】石油系ピツチの加熱時間を20分乃至４時間
とし又10kg/cm²乃至150kg/cm²の加圧を採用する特許請
求の範囲の第１項目の製造法。2. The method according to claim 1, wherein the heating time of the petroleum-based pitch is 20 minutes to 4 hours and a pressure of 10 kg / cm ^{2 to} 150 kg / cm ² is adopted.