JPS63219630A - Production of carbon fiber - Google Patents
Production of carbon fiberInfo
- Publication number
- JPS63219630A JPS63219630A JP5159687A JP5159687A JPS63219630A JP S63219630 A JPS63219630 A JP S63219630A JP 5159687 A JP5159687 A JP 5159687A JP 5159687 A JP5159687 A JP 5159687A JP S63219630 A JPS63219630 A JP S63219630A
- Authority
- JP
- Japan
- Prior art keywords
- source compound
- heating zone
- compound
- carbon source
- carrier gas
- 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
- 229920000049 Carbon (fiber) Polymers 0.000 title claims description 22
- 239000004917 carbon fiber Substances 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 239000012159 carrier gas Substances 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 17
- 239000000835 fiber Substances 0.000 abstract description 7
- 150000003623 transition metal compounds Chemical class 0.000 abstract description 5
- 229920001410 Microfiber Polymers 0.000 abstract 1
- -1 alkane compounds Chemical class 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000004071 soot Substances 0.000 description 4
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 150000002898 organic sulfur compounds Chemical class 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 2
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- LYTMVABTDYMBQK-UHFFFAOYSA-N 2-benzothiophene Chemical compound C1=CC=CC2=CSC=C21 LYTMVABTDYMBQK-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002023 dithiocarboxylic acids Chemical class 0.000 description 1
- CYMVZQRBRVFASM-UHFFFAOYSA-L ethanethioate;iron(2+) Chemical compound [Fe+2].CC([O-])=S.CC([O-])=S CYMVZQRBRVFASM-UHFFFAOYSA-L 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 150000003450 sulfenic acids Chemical class 0.000 description 1
- 150000003455 sulfinic acids Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical class CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003564 thiocarbonyl compounds Chemical class 0.000 description 1
- 150000003565 thiocarboxylic acid derivatives Chemical class 0.000 description 1
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000012808 vapor phase 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、炭素繊維の製造方法に関し、さらに詳しくは
遷移全屈化合物等を触媒源として炭素源化合物等を反応
させ、加熱帯空間で繊維を生成させる炭素繊維の製造方
法に関する。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for producing carbon fibers, and more specifically, the present invention relates to a method for producing carbon fibers, and more specifically, the present invention relates to a method for producing carbon fibers, and more specifically, reacts a carbon source compound, etc. using a transition total bending compound, etc. as a catalyst source, and produces carbon fibers in a heating zone space. The present invention relates to a method for producing carbon fiber.
（従来の技術〕
炭素繊維は高強度、高弾性率などの優れた性質を有し、
各種複合材料として近年脚光を浴びている材料である。(Prior art) Carbon fiber has excellent properties such as high strength and high modulus of elasticity.
It is a material that has been in the spotlight in recent years as a variety of composite materials.
従来、炭素繊維は有機繊維を炭化することによって主に
製造されているが、炭化水素類の熱分解および触媒反応
によって生成する炭素繊維も知られている。後者の気相
法炭素繊維は前者の炭素繊維に較べ、優れた結晶性、配
向性を有しているため、高強度、高弾性率を兼備する複
合材料として、多方面の用途が期待されている。Conventionally, carbon fibers have been mainly produced by carbonizing organic fibers, but carbon fibers produced by thermal decomposition and catalytic reactions of hydrocarbons are also known. The latter type of vapor-grown carbon fiber has superior crystallinity and orientation compared to the former type, so it is expected to be used in a wide variety of fields as a composite material that has both high strength and high modulus. There is.
気相法による炭素繊維の一般的製造法は、例えば［工業
材料、昭和５７年７月号、１０９頁（遠藤、小山）」に
示されているように、遷移金属からなる微粒子を散布し
た繊維生成用基材を電気炉の反応管内に設置し、炉温を
所定温度にした後、反応管内に炭化水素と水素の混合ガ
スを通して炭化させ、基材上に炭素繊維を生成せしめる
ものである。A general method for manufacturing carbon fibers using the vapor phase method is, for example, as shown in [Kogyo Materials, July 1980 issue, p. 109 (Endo, Koyama)], fibers sprinkled with fine particles made of transition metals are used. A production base material is placed in a reaction tube of an electric furnace, and after the furnace temperature is brought to a predetermined temperature, a mixed gas of hydrocarbon and hydrogen is passed through the reaction tube to carbonize, thereby producing carbon fibers on the base material.
しかしながら、このような基材を用いる方法では、反応
域が二次元であることや、プロセスが複雑であることな
どから生産性が低いものであった。However, the method using such a base material has low productivity because the reaction zone is two-dimensional and the process is complicated.
これに対して特開昭５８−１８０６１５号公報には、高
融点全屈または該全屈の化合物の超微粉末を炭化水素の
熱分解帯域に浮遊させる方法が記載されているが、超微
粉末が二次粒子を形成し易く、触媒効果が発揮しにくい
こと等から生産性に優れた方法とはいえなかった。On the other hand, JP-A No. 58-180615 describes a method in which ultrafine powder of a high melting point or compound having a high melting point is suspended in a thermal decomposition zone of hydrocarbons. This method could not be said to have excellent productivity because it was easy to form secondary particles and the catalytic effect was difficult to exhibit.
一方、特開昭６０−５４９９８号、特開昭６０−１８１
３１１号、特開昭６０−１８５８１８号、特開昭６０−
２２４８１５号、特開昭６０−２２４８１６号には、遷
移金属化合物のガス、炭素源化合物のガスおよびキャリ
ヤガスの混合ガスを高温反応させる方法が記載されてい
る。しかしながらこれらの方法は用いる遷移金属化合物
の量が炭素源化合物に対して非常に多く、また収率の低
いものであった。また、アスペクト比が２００以上の炭
素繊維の製造方法としても、さらに生産性の低いもので
あった。On the other hand, JP-A-60-54998, JP-A-60-181
No. 311, JP-A-60-185818, JP-A-60-
No. 224815 and JP-A No. 60-224816 describe a method of subjecting a mixed gas of a transition metal compound gas, a carbon source compound gas, and a carrier gas to a high-temperature reaction. However, in these methods, the amount of the transition metal compound used was much larger than the carbon source compound, and the yield was low. Moreover, even as a method for producing carbon fibers having an aspect ratio of 200 or more, the productivity was even lower.
〔発明が解決しようとする問題点〕
本発明の目的は、極細でアスペクト比の大きい炭素繊維
を生産性および収率よく製造する方法を提供することに
ある。[Problems to be Solved by the Invention] An object of the present invention is to provide a method for producing ultrafine carbon fibers with high aspect ratios with good productivity and yield.
本発明は、炭素源化合物、触媒源化合物、キャリヤガス
および硫黄化合物を加熱帯に供給して炭素繊維を製造す
る方法において、加熱帯温度が１２００℃以上で、単位
時間当たりに加熱帯に供給するキャリヤガス５ｉｆ （
ｍ ｏ ｌ ）が炭素源化合物の単位時間当たりの供給
量ｔ（ｇ）に対して０．２６ ｍｏ ｌ ／ ｇ以上で
あり、供給する炭素源化合物に対する触媒源化合物の量
が０．０１〜ｌ Ｑｗｔ％であることを特徴とする炭素
繊維の製造方法である。The present invention provides a method for producing carbon fiber by supplying a carbon source compound, a catalyst source compound, a carrier gas, and a sulfur compound to a heating zone, in which the heating zone temperature is 1200° C. or higher, and the sulfur compound is supplied to the heating zone per unit time. Carrier gas 5if (
mol) is 0.26 mol/g or more with respect to the supply amount t (g) of the carbon source compound per unit time, and the amount of the catalyst source compound with respect to the supplied carbon source compound is 0.01 to 1 This is a method for producing carbon fiber characterized by Qwt%.
本発明によれば、上記特定の条件で炭素繊維を製造する
ことにより、繊維径が０．５μ以下、特に０．３μ以下
でアスペクト比が２００以上の炭素繊維を得ることがで
きる。この炭素繊維はシートになり易く、非常に成形性
に優れていることが判明した。またシートにしたものを
樹脂を含浸したところ、補強効果および電気、熱伝導性
に優れていることが判明した。According to the present invention, carbon fibers having a fiber diameter of 0.5 μm or less, particularly 0.3 μm or less and an aspect ratio of 200 or more can be obtained by manufacturing carbon fibers under the above-described specific conditions. It was found that this carbon fiber can be easily formed into a sheet and has excellent moldability. Furthermore, when a sheet was impregnated with resin, it was found to have excellent reinforcing effects and excellent electrical and thermal conductivity.
本発明における炭素源化合物とは、８００〜２５００℃
に加熱することによって炭素を析出し得る化合物をいい
、炭素化合物全般を対象としている。例えばｃｏ、メタ
ン、エタン等のアルカン化合物、エチレン、ブクジエン
等のアルケン化合物、アセチレン等のアルキン化合物、
ベンゼン、トルエン、スチレン、ナフタレン、アントラ
セン等の芳香族化合物、シクロヘキサン、シクロベンク
ジエン、ジシクロペンクジエン等の脂環式炭化水素化合
物、またはこれらの窒素、酸素、ハロゲ７％の誘導体、
ガソリン、灯油、重油等があげられ、これらの混合物も
用いることができる。The carbon source compound in the present invention is 800 to 2500°C
It refers to a compound that can precipitate carbon when heated to a certain temperature, and covers all carbon compounds. For example, alkane compounds such as co, methane, and ethane; alkene compounds such as ethylene and bucdiene; alkyne compounds such as acetylene;
Aromatic compounds such as benzene, toluene, styrene, naphthalene, anthracene, etc., alicyclic hydrocarbon compounds such as cyclohexane, cyclobencdiene, dicyclopencdiene, or derivatives thereof containing 7% nitrogen, oxygen, and halogen;
Examples include gasoline, kerosene, heavy oil, etc., and mixtures thereof can also be used.
加熱帯６ぎ供給する炭素源化合物の量（ｇ）は、加熱帯
の体積１１に対して、１分間に０．０５ｇ／ｌ・分以上
が好ましく、特に０．５〜２０．０ｇ／ｌ・分がより好
ましい。炭素源化合物の供給量が少なすぎると充分な生
産性が得られない傾向にあり、多すぎると収率が低下す
る傾向にある。The amount (g) of the carbon source compound supplied to the heating zone is preferably 0.05 g/l·min or more per minute, particularly 0.5 to 20.0 g/l·min, based on the volume 11 of the heating zone. minutes is more preferred. If the amount of the carbon source compound supplied is too small, sufficient productivity tends to not be obtained, and if it is too large, the yield tends to decrease.
本発明における触媒源化合物とは、Ｆ ｅ Ｃ１３、Ｆ
ｅ （Ｎｏ）４、ＮｉＣｌ２、Ｃｏ （Ｎｏ）２ Ｃ４
等の無機遷移金属化合物、Ｆｅ （Ｃ５Ｈｓ）２、Ｎｉ
（ＣＳＨｓ）ｚ、Ｃｏ （Ｃ５Ｈ５）２、Ｆｅ（Ｃ
ｏ）ｓ 、Ｆｅ２ （Ｃｏ）１ 、Ｎｉ （Ｃｏ）
４等の有機遷移金属化合物、アセチルアセトン鉄、カル
ボン酸鉄、鉄アルコキシド、鉄子り−ルオキシド、ニッ
ケルチオアルコキシド、コバルトアルコキシド、チオ酢
酸鉄等の遷移金属化合物等が用いられる。これら触媒源
化合物は２種以上同時に用いてもよい。さらに触媒源化
合物として、特開昭６０−５４９９８号、特開昭６０−
５４９９９号、特開昭６０−１８１３１９号、特開昭６
０−１８５８１８号、特開昭６０−２２４８１５号、特
開昭６０−２２４８１６号、特開昭６０−２３１８２２
号、特開昭６１−１０８７２３号、特開昭６１−２２５
３２２号、特開昭６１−２２５３２７号、特開昭６１−
２７５４２５号、特願昭６０−１２３２０１号等に記載
されている化合物を用いてもよい。The catalyst source compound in the present invention is F e C13, F
e (No)4, NiCl2, Co (No)2 C4
Inorganic transition metal compounds such as Fe (C5Hs)2, Ni
(CSHs)z, Co (C5H5)2, Fe(C
o)s, Fe2(Co)1, Ni(Co)
Transition metal compounds such as iron acetylacetonate, iron carboxylate, iron alkoxide, iron chloride, nickel thioalkoxide, cobalt alkoxide, iron thioacetate, etc. are used. Two or more of these catalyst source compounds may be used simultaneously. Furthermore, as a catalyst source compound, JP-A-60-54998, JP-A-60-
No. 54999, JP-A-60-181319, JP-A-6
0-185818, JP 60-224815, JP 60-224816, JP 60-231822
No., JP-A-61-108723, JP-A-61-225
No. 322, JP-A-61-225327, JP-A-61-
Compounds described in Japanese Patent Application No. 275425, Japanese Patent Application No. 123201/1986, etc. may also be used.
本発明において、触媒源化合物の量は、供給する炭素源
化合物に対して０．０１〜１０ｗｔ％である。触媒源化
合物の量は、これより多くても、少なくても煤が混入し
てくる傾向にある。特に０．１〜５ｗｔ％がより好まし
く用いられる。In the present invention, the amount of the catalyst source compound is 0.01 to 10 wt% based on the carbon source compound supplied. Even if the amount of the catalyst source compound is greater or less than this, soot tends to be mixed in. In particular, 0.1 to 5 wt% is more preferably used.
本発明におけるキャリヤガスとは、■−■２ガス、Ｈｅ
ガス、Ｎ２ガス、Ｎｅガス、Ａｒガス、Ｋｒガス、Ｃ０
２ガス、ＮＨ３ガスを主体とするガスであり、これらの
混合物を用いてもよい。The carrier gas in the present invention refers to ■-■2 gas, He
Gas, N2 gas, Ne gas, Ar gas, Kr gas, C0
The gas is mainly composed of 2 gas and NH3 gas, and a mixture of these gases may also be used.
本発明において、単位時間当たりに加熱帯に供給するキ
ャリヤガス量（ｍｏりは、炭素源化合物の単位時間当た
りの供給量（ｇ）に対して０．２５ ｍ ｏβ／ｇ以上
である。キャリヤガス量が０３２５ｍｏβ／ｇ未満だと
得られる繊維は長さが３０μｍ以下のものが多くなり、
また繊維径が太くなる傾向にある。キャリヤガス量は０
．３０〜５．０ｍｏ １ ／ ｇが好ましく、特に０．
３５〜２．０ｍｏ ｊ２／ｇが好ましい。キャリヤガス
量が多すぎると収率が低下する傾向がある。In the present invention, the amount of carrier gas supplied to the heating zone per unit time (Mo is 0.25 m oβ/g or more with respect to the amount of carbon source compound supplied per unit time (g).Carrier gas When the amount is less than 0325moβ/g, the fibers obtained tend to have a length of 30μm or less,
Furthermore, the fiber diameter tends to become thicker. Carrier gas amount is 0
．． 30 to 5.0 mo 1 / g is preferable, especially 0.0 mo 1 / g.
35 to 2.0 mo j2/g is preferred. If the amount of carrier gas is too large, the yield tends to decrease.
キャリヤガスは、用いる炭素源化合物によっても異なる
が、３ＱｖｏＪ％以上を水素ガスとするのが好ましく、
特に５０ｖＯβ％以上とするのが好ましい。水素ガスが
少ないと得られる繊維の長さが短くなる傾向にある。水
素ガス以外のキャリヤガス成分としては窒素ガス等があ
げられる。Although the carrier gas varies depending on the carbon source compound used, it is preferable that 3QvoJ% or more is hydrogen gas,
In particular, it is preferable to set it to 50vOβ% or more. When the amount of hydrogen gas is low, the length of the fibers obtained tends to be short. Examples of carrier gas components other than hydrogen gas include nitrogen gas and the like.
本発明における硫黄化合物としては、硫化水素、二硫化
炭素および有機硫黄化合物などがあげられ、特に有機硫
黄化合物が好ましく用いられる。有機硫黄化合物として
は、メチルチオール、エチルチオール、ブチルチオール
、フェニルチオール等のチオール類、ジメチルスルフィ
ド、ジエチルスルフィド、フェニルメチルスルフィド等
のスルフィド類、ジメチルスルホキシド、ジエチルスル
ホキシド、ジフェニルスルホキシド等のスルホキシド類
、ジメチルスルホン、ジエチルスルホン等のスルホン類
、チオフェン、イソベンゾチオフェン等の含硫黄複素環
化合物、その他、スルフェン酸類、スルフェン酸エステ
ル類、スルホン酸類、スルホン酸エステルおよびその無
水物等、スルフィン酸類、スルフィン酸エステル類、チ
オールスルフィナート類、チオカルボニル化合物、チオ
カルボン酸類、チオカルボン酸エステル類、ジチオカル
ボン酸類、スルフィン類、チオカルボン酸誘導体Ｓ−オ
キシド類、スルホニウムイリド類、スルフラン類等があ
げられる。これらは１種または２種以上組合わせて用い
られる。Examples of the sulfur compound in the present invention include hydrogen sulfide, carbon disulfide, and organic sulfur compounds, with organic sulfur compounds being particularly preferably used. Examples of organic sulfur compounds include thiols such as methylthiol, ethylthiol, butylthiol, and phenylthiol; sulfides such as dimethyl sulfide, diethyl sulfide, and phenylmethyl sulfide; sulfoxides such as dimethyl sulfoxide, diethyl sulfoxide, and diphenyl sulfoxide; and dimethyl Sulfones such as sulfone and diethylsulfone, sulfur-containing heterocyclic compounds such as thiophene and isobenzothiophene, other sulfenic acids, sulfenic esters, sulfonic acids, sulfonic esters and their anhydrides, sulfinic acids, sulfinic esters, etc. Examples include thiol sulfinates, thiocarbonyl compounds, thiocarboxylic acids, thiocarboxylic acid esters, dithiocarboxylic acids, sulfines, thiocarboxylic acid derivatives S-oxides, sulfonium ylides, sulfurans, and the like. These may be used alone or in combination of two or more.
加熱帯に供給する硫黄化合物の量（ｍｏｆｆ）は、供給
する炭素源化合物の質量（ｇ）に対して１×１０””ｍ
ｏｆ／ｇ以上、ＩＸｌ ０−２ｍｏ １７ｇ以下が好ま
しく、特にＩ Ｘ Ｉ Ｏ−５ｍｏ １７ｇ以上、２Ｘ
Ｉ Ｏ−３ｍｏ ７！／ｇ以下がより好ましい。硫黄
化合物の量が多すぎても少なすぎても煤の混入が多くな
る傾向がある。The amount (moff) of the sulfur compound supplied to the heating zone is 1×10""m relative to the mass (g) of the carbon source compound supplied.
of/g or more, IXI 0-2mo 17g or less is preferable, especially IXI O-5mo 17g or more, 2X
I O-3mo 7! /g or less is more preferable. If the amount of sulfur compounds is too large or too small, there is a tendency for more soot to be mixed in.
本発明における加熱帯温度は１２００℃以上であり、具
体的には反応容器の内壁温度が１２００℃以上に加熱さ
れる。このうち１２５０〜２５００℃、特に１３００〜
２５００℃がより好ましい。The heating zone temperature in the present invention is 1200°C or higher, and specifically, the inner wall temperature of the reaction vessel is heated to 1200°C or higher. Among these, 1250~2500℃, especially 1300~
2500°C is more preferred.
温度が低いと生産性および収率が低下し、高いと煤が混
入する傾向がある。加熱方法については特に限定されな
いが、例えば電気炉加熱、赤外線加熱、プラズマ加熱、
レーザー加熱、燃焼熱利用、反応熱利用等いずれを用い
てもよい。このうち、電気炉加熱が便利である。Lower temperatures reduce productivity and yield, while higher temperatures tend to result in soot contamination. There are no particular limitations on the heating method, but examples include electric furnace heating, infrared heating, plasma heating,
Any of laser heating, combustion heat utilization, reaction heat utilization, etc. may be used. Among these, electric furnace heating is convenient.
炭素源化合物、触媒源化合物、キャリヤガスおよび硫黄
化合物を加熱帯に供給する方法は、特に限定されず、例
えばそれぞれをガスで供給する方法、混合ガスで供給す
る方法、液状で供給する方法、混合液状で供給する方法
、粉末状で供給する方法、これらの組合わせ等いずれの
方法を用いてもよい。The method of supplying the carbon source compound, the catalyst source compound, the carrier gas, and the sulfur compound to the heating zone is not particularly limited. For example, each of them can be supplied as a gas, as a mixed gas, as a liquid, or as a mixture. Any method such as a method of supplying in liquid form, a method of supplying in powder form, or a combination thereof may be used.
本発明によれば、機械強度が優れ、シートになり易く、
成形性に優れた、極細でアスペクト比の大きな炭素繊維
を、生産性および収率よく、また煤の混入がほとんどな
く製造することができる。According to the present invention, it has excellent mechanical strength, can be easily formed into a sheet,
Ultra-fine carbon fibers with excellent moldability and a large aspect ratio can be produced with good productivity and yield, and with almost no soot contamination.
実施例１〜９、比較例１〜３
第１図に示したように、電気炉１ （均熱長１２０ＣＩ
１１）に黒鉛チューブ２ （内径６０鶴、長さ１８００
ｃｍ）を設置し、黒鉛チューブ２の一端にボックス３を
接続し、ボックス１内にフィルタ７を設置して生成物を
収集できるようにした。また黒鉛チューブ２の弛め一端
には原料を加熱帯に供給するためのパイプ４．５を接続
したノズル６を設置した。Examples 1 to 9, Comparative Examples 1 to 3 As shown in FIG.
11) Graphite tube 2 (inner diameter 60mm, length 180mm
cm) was installed, a box 3 was connected to one end of the graphite tube 2, and a filter 7 was installed inside the box 1 so that the product could be collected. Further, a nozzle 6 connected to a pipe 4.5 for supplying raw material to the heating zone was installed at one loose end of the graphite tube 2.
電気炉１内および黒鉛チューブ２内を窒素置換した後、
黒鉛チューブ２内温度を第１表に示した温度に設定した
。その後キャリヤガス（水素、以下同じ）で黒鉛チュー
ブ内を置換した後、導入パイプ５から黒鉛チューブ２内
にキャリヤガスを導入した。次にベンゼンに第１表に示
す触媒源化合物および硫黄化合物を微分散または熔解さ
せ、バイブ５を経てノズル６よりキャリヤガスとともに
噴霧して黒鉛チューブ２内に供給した。After replacing the inside of the electric furnace 1 and graphite tube 2 with nitrogen,
The temperature inside the graphite tube 2 was set to the temperature shown in Table 1. Thereafter, the inside of the graphite tube was replaced with carrier gas (hydrogen, the same applies hereinafter), and then the carrier gas was introduced into the graphite tube 2 from the introduction pipe 5. Next, the catalyst source compounds and sulfur compounds shown in Table 1 were finely dispersed or dissolved in benzene, and the mixture was sprayed together with a carrier gas from a nozzle 6 via a vibrator 5 and supplied into the graphite tube 2 .
ベンゼン溶液をキャリヤガスとともに１０分間供給した
後、黒鉛チューブ２内にキャリヤガスのみをさらに５分
間供給した。得られた炭素繊維は、走査型および透過型
電子顕微鏡等の観察によりその長さ、径等を測定した。After the benzene solution was supplied together with the carrier gas for 10 minutes, only the carrier gas was supplied into the graphite tube 2 for another 5 minutes. The length, diameter, etc. of the obtained carbon fibers were measured by observation using scanning and transmission electron microscopes.
これらの結果を第１表に示した。These results are shown in Table 1.
第１図は、本発明を実施するための装置の一例を示す説
明図である。
■・・・電気炉、２・・・反応容器、３・・・生成物を
貯蔵するためのボックス、４．５・・・供給パイプ、６
・・・供給ノズル、７・・・フィルタ。
代理人 弁理士 川 北 武 長
第１図FIG. 1 is an explanatory diagram showing an example of an apparatus for implementing the present invention. ■... Electric furnace, 2... Reaction vessel, 3... Box for storing the product, 4.5... Supply pipe, 6
... Supply nozzle, 7... Filter. Agent Patent Attorney Takenaga Kawakita Figure 1
Claims (1)
び硫黄化合物を加熱帯に供給して炭素繊維を製造する方
法において、加熱帯温度が１２００℃以上で、単位時間
当たりに加熱帯に供給するキャリヤガス量（ｍｏｌ）が
炭素源化合物の単位時間当たりの供給量（ｇ）に対して
０．２６ｍｏｌ／ｇ以上であり、供給する炭素源化合物
に対する触媒源化合物の量が０．０１〜１０ｗｔ％であ
ることを特徴とする炭素繊維の製造方法。(1) In a method for producing carbon fiber by supplying a carbon source compound, a catalyst source compound, a carrier gas, and a sulfur compound to a heating zone, the carrier is supplied to the heating zone per unit time when the heating zone temperature is 1200°C or higher. The amount of gas (mol) is 0.26 mol/g or more with respect to the amount (g) of the carbon source compound supplied per unit time, and the amount of the catalyst source compound is 0.01 to 10 wt% with respect to the carbon source compound supplied. A method for producing carbon fiber, characterized by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5159687A JPS63219630A (en) | 1987-03-06 | 1987-03-06 | Production of carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5159687A JPS63219630A (en) | 1987-03-06 | 1987-03-06 | Production of carbon fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63219630A true JPS63219630A (en) | 1988-09-13 |
Family
ID=12891289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5159687A Pending JPS63219630A (en) | 1987-03-06 | 1987-03-06 | Production of carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63219630A (en) |
-
1987
- 1987-03-06 JP JP5159687A patent/JPS63219630A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4876078A (en) | Process for preparing carbon fibers in gas phase growth | |
| TWI383952B (en) | Single-layered carbon nanotube, carbon fiber aggregation containing the same and manufacturing method thereof | |
| JP4968643B2 (en) | Method for producing single-walled carbon nanotube | |
| JP5042333B2 (en) | Crimped carbon fiber and its production method | |
| CN101027434B (en) | Production method of vapor-grown varbon fiber and apparatus therefor | |
| WO2007072584A1 (en) | Vapor-grown carbon fiber and production process thereof | |
| JP4535808B2 (en) | Crimped carbon fiber and its production method | |
| JP2006057231A (en) | Method for producing carbon fiber in gas-phase process and apparatus for producing the same | |
| JP2001080913A (en) | Carbonaceous nanotube, fiber assembly and production of carbonaceous nanotube | |
| JPS63282313A (en) | Ultrafine carbon fiber produced by vapor method | |
| JPS63219630A (en) | Production of carbon fiber | |
| JP4706058B2 (en) | Method for producing a carbon fiber aggregate comprising ultrafine single-walled carbon nanotubes | |
| JPH01298214A (en) | Production of carbon fiber | |
| JPS62282020A (en) | Production of carbon fiber | |
| JPS61282427A (en) | Production of carbonaceous fiber | |
| CN100503913C (en) | Crimped carbon fiber and production method thereof | |
| JPS61225328A (en) | Production of carbonaceous fiber | |
| JP4357163B2 (en) | Fine carbon fiber and composition containing the same | |
| JP2007169838A (en) | Vapor grown carbon fiber and method for producing the same | |
| JPH0665765B2 (en) | Carbon fiber manufacturing method | |
| KR101109046B1 (en) | Cup-stacked Carbon Nanotubes and Method of Preparing Same | |
| JPS62238826A (en) | Production of carbon fiber | |
| JPH02127523A (en) | Carbon fiber of vapor growth | |
| JPH026616A (en) | Production of carbon fiber | |
| JPS61225322A (en) | Production of carbonaceous fiber |