JPS62238826A - Production of carbon fiber - Google Patents
Production of carbon fiberInfo
- Publication number
- JPS62238826A JPS62238826A JP7448086A JP7448086A JPS62238826A JP S62238826 A JPS62238826 A JP S62238826A JP 7448086 A JP7448086 A JP 7448086A JP 7448086 A JP7448086 A JP 7448086A JP S62238826 A JPS62238826 A JP S62238826A
- Authority
- JP
- Japan
- Prior art keywords
- preheating
- source compound
- carrier gas
- carbon
- 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 abstract description 21
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 53
- 239000012159 carrier gas Substances 0.000 claims abstract description 39
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- 239000003054 catalyst Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 21
- 239000007789 gas Substances 0.000 abstract description 23
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000000835 fiber Substances 0.000 abstract description 6
- 239000004071 soot Substances 0.000 abstract description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract 1
- 239000000356 contaminant Substances 0.000 abstract 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- -1 alkane compounds Chemical class 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 150000003623 transition metal compounds Chemical class 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 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
- 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
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 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
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 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
- 150000001722 carbon compounds Chemical class 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
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 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
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910021331 inorganic silicon compound Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IUTZKZLVPUPHDA-UHFFFAOYSA-N n-(4-chlorophenyl)-2h-triazol-4-amine Chemical compound C1=CC(Cl)=CC=C1NC1=NNN=C1 IUTZKZLVPUPHDA-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 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
- 238000010926 purge Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
遷移金属化合物等を触媒源として炭素源化合物を反応さ
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 (Field of Industrial Application) The present invention relates to a method for producing carbon fibers, and more specifically, a method for producing carbon fibers in a heating zone space by reacting a carbon source compound using a transition metal compound as a catalyst source. The present invention relates to a method for manufacturing 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比べ、優れた結晶性、配
向性を有しいているため、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 of carbon fiber, 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 producing carbon fibers using the vapor phase method is to produce fibers sprinkled with fine particles made of transition metals, as shown in, for example, "Kogyo Zazai, July 1980 issue, p. 109 (Endo, Koyama)". 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２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
融点金属または該金属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て炭素繊維を生成させる方法が記
されているが、超微粉末が２次粒子を形成しやすく、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-58-180615 describes a method for producing carbon fibers by suspending ultrafine powder of a high-melting point metal or a compound of the metal in a hydrocarbon thermal decomposition zone. However, this method could not be said to have excellent productivity because the ultrafine powder easily forms secondary particles and the catalytic effect is 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と炭素源化合物のガスとキャリアガ
スと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。また本発明者の検討によれば、時間当
たりの生産量を向上すべく原料供給量を大きくしたとこ
ろ、さらに収率が低下し、煤が混入するという問題を生
じた。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 in which a mixed gas of a transition metal compound gas, a carbon source compound gas, and a carrier gas is subjected to a high temperature reaction. However, in these methods, the amount of the transition metal compound used is much larger than the carbon source compound, and the yield is low. Further, according to studies by the present inventors, when the amount of raw materials supplied was increased in order to improve the production amount per hour, the yield further decreased and problems such as soot contamination occurred.
（発明が解決しようとする問題点）
本発明の目的は、上述の問題点を解決し、生産性および
収率が高く、煤のほとんど混入しない炭素繊維の製造方
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 solve the above-mentioned problems and provide a method for producing carbon fibers that has high productivity and yield and is hardly contaminated with soot.
（問題点を解決するための手段）
すなわち本発明は、炭素源化合物と触媒源化合物および
キャリアガスを加熱帯域に供給する炭素繊維の製造方法
において、少なくともキャリアガスを５００°Ｃ以上に
予熱することを特徴とする炭素繊維の製造方法である。(Means for Solving the Problems) That is, the present invention provides a carbon fiber manufacturing method in which a carbon source compound, a catalyst source compound, and a carrier gas are supplied to a heating zone, including preheating at least the carrier gas to 500°C or higher. This is a method for producing carbon fiber characterized by the following.
本発明における炭素源化合物とは、８００〜１８００℃
に加熱することによって炭素を析出しうる化合物であり
、炭素化合物全般を対象としたものである。例えば、Ｃ
Ｏ、メタン、エタン等のアルカン化合物、エチレン、ブ
タジェ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
ロペンタジェン、ジシクロペンタジェン等の脂環式炭化
水素化合物、またこれらの窒素、酸素、ハロゲン等を含
む誘導体、ガソリン、灯油、重油等が挙げられ、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 1800°C
It is a compound that can precipitate carbon by heating, and is intended for carbon compounds in general. For example, C
O, alkane compounds such as methane and ethane, alkene compounds such as ethylene and butadiene, alkyne compounds such as acetylene, benzene, toluene, styrene, naphthalene,
Examples include aromatic compounds such as anthracene, alicyclic hydrocarbon compounds such as cyclohexane, cyclopentadiene, and dicyclopentadiene, derivatives thereof containing nitrogen, oxygen, halogen, etc., gasoline, kerosene, heavy oil, etc. Mixtures of can also be used.
本発明における触媒源化合物とは、Ｆ ｅ Ｃ７！３、
Ｆｅ （ＮＯ）４、Ｎ１Ｃｊ！ｚ、Ｃｏ （Ｎｏ）２
Ｃβ等の無機遷移金属化合物、Ｆｅ（Ｃ５Ｈｓ）ｚ、Ｎ
ｉ （Ｃｇ Ｈｓ）２、Ｃｏ （Ｃ！ｌ Ｈり２、Ｆ
ｅ（Ｃｏ）ｓ、Ｆｅ２ （Ｃｏ）ｔ、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、鉄アリールオキシド、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、５ｉ（ＣＨ：ｌ）４ 、Ｓ
ｔ （Ｃ２Ｈ５）４ 、ＣＨ３５ｉＣ１３等の有機ケ
イ素化合物または５ｉＣｊ！４、ＳｉＯ等の無機ケイ素
化合物とイオウ化合物（硫化水素、Ｃ８２またはチオー
ル、スルフィド、チオフェン、スルホキシド等の有機イ
オウ化合物）などが挙げられ、これらの混合物を用いて
もよい。The catalyst source compound in the present invention is F e C7!3,
Fe (NO)4, N1Cj! z, Co (No)2
Inorganic transition metal compounds such as Cβ, Fe(C5Hs)z, N
i (Cg Hs)2, Co (C!l Hri2, F
e(Co)s, Fe2(Co)t, Ni(Co)
)4, transition metal compounds such as iron acetylacetonate, iron carboxylate, iron alkoxide, iron aryloxide, nickel thioalkoxide, cobalt alkoxide, iron thioacetate, etc., 5i(CH:l)4, S
Organosilicon compounds such as t (C2H5)4, CH35iC13, or 5iCj! 4. Examples include inorganic silicon compounds such as SiO and sulfur compounds (hydrogen sulfide, C82 or organic sulfur compounds such as thiol, sulfide, thiophene, and sulfoxide), and mixtures thereof may also be used.
炭素源化合物および触媒源化合物は、上記の他に例えば
特開昭６０−５４９９８号、特開昭６０−５４９９９号
、特開昭６０−１８１３１９号、特開昭６０−１８５８
１８号、特開昭６０−２２４８１５号、特開昭６０−２
２４８１６号、特開昭６０−２３１８２２号、特願昭５
９−２３１９６７号、特願昭６０−５８８１３号、特願
昭６゜−５８８１９号、特願昭６０−１１３１０８号、
特願昭６０−１２３２０１号等に記載されているものも
使用可能である。In addition to the above, carbon source compounds and catalyst source compounds include, for example, JP-A-60-54998, JP-A-60-54999, JP-A-60-181319, and JP-A-60-1858.
No. 18, JP-A-60-224815, JP-A-60-2
No. 24816, Japanese Unexamined Patent Publication No. 60-231822, Patent Application No. 1983
9-231967, Japanese Patent Application No. 60-58813, Japanese Patent Application No. 60-58819, Japanese Patent Application No. 113108-1980,
Those described in Japanese Patent Application No. 60-123201 and the like can also be used.
本発明におけるキャリアガスとは、Ｈ２ガス、Ｈｅガス
、Ｎ２ガス、Ｎｅガス、Ａｒガス、Ｋｒガス、ＣＯ□ガ
スまたはＮＨ３ガスを主体とするガスであり、これらの
２種以上の混合物を用いてもよい。The carrier gas in the present invention is a gas mainly composed of H2 gas, He gas, N2 gas, Ne gas, Ar gas, Kr gas, CO□ gas, or NH3 gas, and a mixture of two or more of these gases is used. Good too.
本発明における加熱帯とは、８００℃以上に加熱された
容器の内部空間をいい、特に９００〜１８００℃が好ま
しく用いられる。加熱方法については、電気炉加熱、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が、電気炉加熱が便利である。The heating zone in the present invention refers to the internal space of a container heated to 800°C or higher, and 900 to 1800°C is particularly preferably used. As for the heating method, any of electric furnace heating, plasma heating, laser heating, combustion heat utilization, reaction heat utilization, etc. may be used, but electric furnace heating is convenient.
本発明においては、キャリアガスを少なくとも５００℃
以上に予熱することを特徴とする。ここで予熱とは、炭
素源化合物と触媒源化合物とキャリアガスを混合して８
００℃以上に加熱する前の段階での加熱をいう。予熱す
る方法としては、（ア）キャリアガスのみを単独で予熱
する方法、（イ）炭素源化合物の共存下で予熱する方法
、（つ）触媒源化合物の共存下で予熱する方法、（１）
炭素源化合物と触媒源化合物の共存下で予熱する方法、
（オ）キャリアガスと炭素源化合物とをそれぞれ別々に
予熱する方法、（力）キャリアガスと触媒源化合物をそ
れぞれ別々に予熱する方法、（キ）キャリアガスと炭素
源化合物と触媒源化合物をそれぞれ別々に予熱する方法
等がある。In the present invention, the carrier gas is heated to at least 500°C.
It is characterized by preheating to a higher temperature. Here, preheating refers to mixing a carbon source compound, a catalyst source compound, and a carrier gas.
This refers to heating at a stage before heating to 00°C or higher. The preheating methods include (a) a method of preheating only the carrier gas alone, (b) a method of preheating in the coexistence of a carbon source compound, (ii) a method of preheating in the coexistence of a catalyst source compound, (1)
A method of preheating in the coexistence of a carbon source compound and a catalyst source compound,
(E) A method of preheating the carrier gas and the carbon source compound separately, (A) A method of preheating the carrier gas and the catalyst source compound separately, (G) A method of preheating the carrier gas, the carbon source compound, and the catalyst source compound respectively. There are ways to preheat separately.
キャリアガスのみを単独で予熱する場合、予熱温度は少
なくとも５００℃以上であればよく、上限は特にないが
、反応帯域の炭素源化合物と触媒源化合物とキャリアガ
スの混合状態で１８００℃を超えないのが好ましい。混
合状態で１８００℃を超えると得られる繊維の収率が低
下し、煤の混入が多くなってくる。したがって、５００
℃以上、２０００℃以下が好ましく、７００〜１８００
℃、特に８００〜１５００℃が好ましい。When preheating only the carrier gas, the preheating temperature should be at least 500°C or higher, and there is no particular upper limit, but it does not exceed 1800°C in a mixed state of the carbon source compound, catalyst source compound, and carrier gas in the reaction zone. is preferable. If the temperature exceeds 1800° C. in the mixed state, the yield of fibers obtained will decrease and soot will be mixed in more. Therefore, 500
℃ or higher and 2000℃ or lower, preferably 700 to 1800℃
℃, especially 800 to 1500℃ is preferred.
炭素源化合物共存下で予熱する場合、予熱温度は５００
〜１０００℃が好ましく、５００〜８００℃がより好ま
しい。予熱温度が高いと炭素源化合物の熱分解が予熱段
階で激しくなり、得られる繊維の収率も低下する。When preheating in the coexistence of a carbon source compound, the preheating temperature is 500℃.
-1000 degreeC is preferable, and 500-800 degreeC is more preferable. If the preheating temperature is high, the thermal decomposition of the carbon source compound becomes intense during the preheating stage, and the yield of the obtained fibers also decreases.
触媒源化合物共存下で予熱する場合、一般的には予熱温
度は５００〜２０００℃が好ましく、７００〜１８００
℃がより好ましい。しかしながら、ペンタカルボニル鉄
のように分解温度の低い触媒源化合物共存下で予熱する
場合には、用いる触媒源化合物の量を増やして７００〜
１８００°Ｃに予熱するか、または予熱温度を５００〜
１０００℃にするのが繊維の収率の面から好ましい。When preheating is performed in the coexistence of a catalyst source compound, the preheating temperature is generally preferably 500 to 2000°C, and 700 to 1800°C.
℃ is more preferable. However, when preheating is carried out in the coexistence of a catalyst source compound with a low decomposition temperature such as pentacarbonyl iron, the amount of the catalyst source compound used is increased to
Preheat to 1800°C or increase the preheating temperature to 500°C
The temperature is preferably 1000°C from the viewpoint of fiber yield.
炭素源化合物と触媒源化合物共存下で予熱する場合、予
熱温度は５００〜８００℃がより好ましいが、滞留時間
を３０秒以下、特に５秒以下とするのが好ましい。When preheating is performed in the coexistence of a carbon source compound and a catalyst source compound, the preheating temperature is more preferably 500 to 800°C, but the residence time is preferably 30 seconds or less, particularly 5 seconds or less.
キャリアガスと炭素源化合物とをそれぞれ別々に予熱す
る場合、キャリアガスは５００〜２０００℃が好ましく
、７００〜１８００℃がより好ましい。一方炭素源化合
物は１０００℃以下が好ましく、３００〜８００℃、特
に４００〜７００℃がより好ましい。When preheating the carrier gas and the carbon source compound separately, the carrier gas is preferably 500 to 2000°C, more preferably 700 to 1800°C. On the other hand, the temperature of the carbon source compound is preferably 1000°C or less, more preferably 300 to 800°C, particularly 400 to 700°C.
キャリアガスと触媒源化合物をそれぞれ別々に予熱する
場合、キャリアガスの予熱は５００〜２０００℃、特に
７００〜１８００″Ｃが好ましい。When the carrier gas and the catalyst source compound are preheated separately, the preheating of the carrier gas is preferably from 500 to 2000°C, particularly from 700 to 1800''C.
一方触媒源化合物の予熱は１０００℃以下が好ましく、
特に３００〜９００℃が好ましい。On the other hand, the preheating of the catalyst source compound is preferably 1000°C or less,
Particularly preferred is 300 to 900°C.
キャリアガスと炭素源化合物と触媒源化合物をそれぞれ
別々に予熱する場合、キャリアガスは５００〜２０００
℃、特に７００〜１８００℃が好ましく、炭素源化合物
は３００〜８００℃、特に４００〜７００“Ｃが好まし
く、触媒源化合物は３００〜９００℃が好ましい。When preheating the carrier gas, carbon source compound, and catalyst source compound separately, the carrier gas has a temperature of 500 to 2000
C, especially 700 to 1800 C, the carbon source compound is preferably 300 to 800 C, especially 400 to 700 C, and the catalyst source compound is preferably 300 to 900 C.
キャリアガスの導入方法としては、単独で導入する方法
以外に、炭素源化合物とともに導入する方法、触媒源化
合物とともに導入する方法、炭素源化合物と触媒源化合
物とともに導入する方法、またはこれらの組合わせが可
能である。本発明において、これらの組合わせの場合に
は、それぞれのキャリアガスの熱量を合計したものが、
５００℃以上（好ましくは７００〜１８００℃）の熱量
に対応すればよい。ただし本発明において熱量の計算に
は、３００℃における定圧比熱を用いる。In addition to introducing the carrier gas alone, the carrier gas may be introduced together with a carbon source compound, a catalyst source compound, a carbon source compound and a catalyst source compound, or a combination thereof. It is possible. In the present invention, in the case of these combinations, the total calorific value of each carrier gas is
It is sufficient to handle a heat amount of 500°C or higher (preferably 700 to 1800°C). However, in the present invention, constant pressure specific heat at 300° C. is used to calculate the amount of heat.
本発明において好ましい予熱の方法は、キャリアガスの
みを５００℃以上、特に７００〜１８００℃に予熱し、
かつ、炭素源化合物と触媒源化合物またはその導入に用
いるキャリアガスを３００〜８００℃、特に４００〜７
００℃に予熱する方法、もしくはキャリアガスのみを５
００℃以上、特に７００−１８００℃に予熱する方法で
ある。A preferred preheating method in the present invention is to preheat only the carrier gas to 500°C or higher, particularly 700 to 1800°C,
And, the carbon source compound and the catalyst source compound or the carrier gas used for introducing them are heated at 300 to 800°C, especially 400 to 700°C.
Preheating to 00℃ or heating only the carrier gas to 5℃
This is a method of preheating to 00°C or higher, especially 700-1800°C.
本発明の作用機構については明らかではないが、キャリ
アガスの予熱により、触媒源の活性化および副反応の抑
制に効果があると思われる。Although the mechanism of action of the present invention is not clear, it is believed that preheating the carrier gas is effective in activating the catalyst source and suppressing side reactions.
（発明の効果）
本発明の方法によれば、煤のほとんど混入していない炭
素繊維を収率よく得ることができる。また原料供給量を
多くしても同様に煤のほとんど混入していない炭素繊維
が収率よ（得られ、時間当たりの生産量を大きく向上さ
せることができる。(Effects of the Invention) According to the method of the present invention, carbon fibers containing almost no soot can be obtained in good yield. Furthermore, even if the amount of raw material supplied is increased, carbon fibers containing almost no soot can be obtained at a higher yield, and the production amount per hour can be greatly improved.
（実施例）
実施例■
本発明を実施するための好ましい装置の一例を第１図に
示した。この装置は、内径９０重層の反応容器（アルミ
ナチューブ）２を有する電気炉１ （加熱帯の長さ１ｍ
）と、その一端に接続された炭素繊維貯蔵用のボックス
３とからなる。アルミナチューブ２の他の一端には、キ
ャリアガス導入パイプ４と炭素源および触媒源の導入バ
イブロが挿入され、それぞれのパイプには予熱ヒーター
５および７が設けられている。(Example) Example (2) An example of a preferred apparatus for carrying out the present invention is shown in FIG. This device consists of an electric furnace 1 (heating zone length 1 m) having a reaction vessel (alumina tube) 2 with an inner diameter of 90 layers
) and a carbon fiber storage box 3 connected to one end of the box. A carrier gas introduction pipe 4 and a carbon source and catalyst source introduction vibro are inserted into the other end of the alumina tube 2, and preheating heaters 5 and 7 are provided in each pipe.
反応器（アルミナチューブ）２内とボックス３内をＮ２
ガスで置換後、反応器２内を１２００℃とした後、Ｎ２
ガスで置換した。パイプ４からＮ２ガス３０２７分（室
温でのガス流ｉｔ）を導入し、ヒーター５を通過する間
に１２００℃に予熱し、加熱帯域に導入した。その後、
アセチルアセトン鉄（Ｑ、４ｗｔ％）とチオフェン（０
，２ｗｔ％）のベンゼン溶液を１５ｇ／分でバイブロか
らヒーター７の部分へ導入し、５００℃に予熱した後、
加熱帯域へ１０分間供給した。その結果、ボックス３に
直径０．２μ以下で長さ３００μの細い炭素繊維が８４
ｇ得られた。N2 inside reactor (alumina tube) 2 and box 3
After purging with gas, the inside of reactor 2 was heated to 1200°C, and then replaced with N2
Replaced with gas. 3027 minutes of N2 gas (gas flow it at room temperature) was introduced through pipe 4, preheated to 1200° C. while passing through heater 5, and introduced into the heating zone. after that,
Iron acetylacetonate (Q, 4 wt%) and thiophene (0
, 2 wt%) was introduced from the vibro to the heater 7 at a rate of 15 g/min, and after preheating to 500°C,
The heating zone was fed for 10 minutes. As a result, 84 thin carbon fibers with a diameter of 0.2μ or less and a length of 300μ were placed in box 3.
g was obtained.
実施例２〜４、比較例１〜２
Ｈｚガスの予熱温度を種々変化させた以外は、実施例１
と同様に行なった。これらの結果を第１表に示した。Examples 2 to 4, Comparative Examples 1 to 2 Example 1 except that the preheating temperature of the Hz gas was variously changed.
I did the same thing. These results are shown in Table 1.
第 １ 表
実施例５〜７
ベンゼン溶液を霧化させてＮ２ガス５１７分でヒーター
２へ１股送し、種々の温度に加熱した以外は実施例１と
同様に行なった。これらの結果を第１表に示した。Table 1 Examples 5 to 7 The same procedure as in Example 1 was carried out, except that the benzene solution was atomized and fed to the heater 2 for 517 minutes with N2 gas, and heated to various temperatures. These results are shown in Table 1.
実施例８〜１１、比較例３〜５
反応器として内径６０ｍのムライトチューブ２を第１図
のように設置し、キャリアガスとしてＨ２とＮ２にＨ２
ＳをＩＶｏｊｌ！％混合したものを用いた。また炭素源
としてベンゼン、触媒源としてフェロセンをベンゼンに
０．５ ｗ ｔ％ン容解させたものを用い、種々条件を
変化させて１０分間反応を行なった。これらの結果を第
２表に示す。Examples 8 to 11, Comparative Examples 3 to 5 A mullite tube 2 with an inner diameter of 60 m was installed as a reactor as shown in Fig. 1, and H2 and N2 were added as carrier gases.
IVojl S! % mixture was used. Further, using benzene as a carbon source and 0.5 wt % of ferrocene dissolved in benzene as a catalyst source, the reaction was carried out for 10 minutes under various conditions. These results are shown in Table 2.
以下余白 ＊ 炭素源導入ノズルが詰まりかけた。Margin below *The carbon source introduction nozzle was about to become clogged.
実施例１２〜１４
反応器として内径１００ｍのムライトチューブ２を用い
、第２図のように、らせん状に巻いた石英チューブ８（
内径５ｎ）にキャリアガスを通して電気炉内で１１００
℃まで予熱し、入口９から反応器内に導入した。一方、
炭素源としてベンゼンまたはプロパンをチューブ１０か
らＨ２ガスで搬送し、予熱ヒーター２で４００℃まで予
熱した。Examples 12 to 14 A mullite tube 2 with an inner diameter of 100 m was used as a reactor, and as shown in FIG. 2, a spirally wound quartz tube 8 (
1100 in an electric furnace by passing carrier gas through the inner diameter 5n).
It was preheated to ℃ and introduced into the reactor through inlet 9. on the other hand,
Benzene or propane as a carbon source was conveyed with H2 gas through a tube 10 and preheated to 400° C. with a preheating heater 2.
また触媒源としてフェロセンをガス化させ、チューブ１
１からＨ２とともにヒーター２に搬送し、４００℃まで
予熱した後、これらを反応器２に導入し、１０分間反応
を行なった。これらの結果を第３表に示した。In addition, ferrocene is gasified as a catalyst source, and tube 1
1 to the heater 2 together with H2 and preheated to 400° C., then introduced into the reactor 2 and reacted for 10 minutes. These results are shown in Table 3.
第３表
キャリアガス流量 水 炭素源
（１／分） 触媒 収量収率導
入量 備考
炭素源 触媒源石英チ 用いた化導入量の搬送 の搬送
エーゾ 合物 （ｇ／（ｇ（に用い に
用い で予熱 ｇた量 た量 した量
実施例 ０１５ プロパン １０ ０．５
４０ ４９ わず実施例 １ １ １
０ − １．０ ０．１ ４２ ５１
実施例１５〜１６、比較例６〜７
反応器として内径３０ｍのアルミナチューブ２を第１図
のように設置し、炭素源としてトルエン、キャリアガス
としてＨ２ガス、触媒源としてニラケロセンを用い、ニ
ラケロセンをトルエンに対して０．０５ ｗ ｔ％溶解
させ、１０分間反応を行なった。これらの結果を第４表
に示した。Table 3 Carrier gas flow rate Water Carbon source (1/min) Catalyst Yield Yield Amount introduced Notes Carbon source Catalyst source Quartz Preheating g Amount Amount Amount Example 015 Propane 10 0.5
40 49 Example 1 1 1
0 - 1.0 0.1 42 51
Examples 15-16, Comparative Examples 6-7 An alumina tube 2 with an inner diameter of 30 m was installed as a reactor as shown in Fig. 1, toluene was used as a carbon source, H2 gas was used as a carrier gas, and nilakerosene was used as a catalyst source. It was dissolved in toluene at 0.05 wt% and reacted for 10 minutes. These results are shown in Table 4.
第１〜４表の結果から、反応器の断面積が大きいほど、
本発明の効果がより顕著になる傾向が見られた。From the results in Tables 1 to 4, the larger the cross-sectional area of the reactor, the more
There was a tendency for the effects of the present invention to become more pronounced.
第４表Table 4
第１図および第２図は、それぞれ本発明を実施するため
の好ましい装置の説明図である。
１・・・電気炉、２・・・反応器、３・・・炭素繊維貯
蔵ボックス、４．６．１０．１１・・・導入パイプ、５
．７．１２・・・予熱ヒーター、８・・・石英チューブ
、９・・・キャリアガス導入口。
代理人 弁理士 川 北 武 長
第１図1 and 2 are illustrations of preferred apparatus for carrying out the invention, respectively. 1... Electric furnace, 2... Reactor, 3... Carbon fiber storage box, 4.6.10.11... Introduction pipe, 5
．． 7.12... Preheating heater, 8... Quartz tube, 9... Carrier gas inlet. Agent Patent Attorney Takenaga Kawakita Figure 1
Claims (1)
を加熱帯域に供給し、炭素繊維を製造する方法において
、少なくともキャリアガスを５００℃以上に予熱するこ
とを特徴とする炭素繊維の製造方法。(1) A method for producing carbon fibers by supplying a carbon source compound, a catalyst source compound, and a carrier gas to a heating zone, the method comprising preheating at least the carrier gas to 500° C. or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7448086A JPS62238826A (en) | 1986-04-01 | 1986-04-01 | Production of carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7448086A JPS62238826A (en) | 1986-04-01 | 1986-04-01 | Production of carbon fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62238826A true JPS62238826A (en) | 1987-10-19 |
Family
ID=13548475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7448086A Pending JPS62238826A (en) | 1986-04-01 | 1986-04-01 | Production of carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62238826A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0280619A (en) * | 1988-09-12 | 1990-03-20 | Nkk Corp | Production of carbon fiber |
| WO2003002789A1 (en) * | 2001-06-28 | 2003-01-09 | Showa Denko K.K. | Method and apparatus for producing vapor grown carbon fiber |
| JP2005015339A (en) * | 2000-04-12 | 2005-01-20 | Showa Denko Kk | Fine carbon fiber, method of manufacturing the same and conductive material containing fine carbon fiber |
-
1986
- 1986-04-01 JP JP7448086A patent/JPS62238826A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0280619A (en) * | 1988-09-12 | 1990-03-20 | Nkk Corp | Production of carbon fiber |
| JP2005015339A (en) * | 2000-04-12 | 2005-01-20 | Showa Denko Kk | Fine carbon fiber, method of manufacturing the same and conductive material containing fine carbon fiber |
| WO2003002789A1 (en) * | 2001-06-28 | 2003-01-09 | Showa Denko K.K. | Method and apparatus for producing vapor grown carbon fiber |
| US7524479B2 (en) | 2001-06-28 | 2009-04-28 | Showa Denko K.K. | Method for producing vapor grown carbon fiber |
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