JPS62282020A - Production of carbon fiber - Google Patents
Production of carbon fiberInfo
- Publication number
- JPS62282020A JPS62282020A JP12078986A JP12078986A JPS62282020A JP S62282020 A JPS62282020 A JP S62282020A JP 12078986 A JP12078986 A JP 12078986A JP 12078986 A JP12078986 A JP 12078986A JP S62282020 A JPS62282020 A JP S62282020A
- Authority
- JP
- Japan
- Prior art keywords
- source compound
- heating zone
- compound
- carrier gas
- carbon source
- 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 23
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 23
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 239000012159 carrier gas Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 11
- -1 FeCl3 Chemical class 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 16
- 239000004071 soot Substances 0.000 abstract description 12
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 abstract description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005977 Ethylene Substances 0.000 abstract description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 abstract description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 150000003623 transition metal compounds Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000002898 organic sulfur compounds Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 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
- CETBSQOFQKLHHZ-UHFFFAOYSA-N Diethyl disulfide Chemical compound CCSSCC CETBSQOFQKLHHZ-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 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
- 229930192474 thiophene Natural products 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
- 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
- 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
- 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
- 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
- 238000011109 contamination Methods 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- 150000002023 dithiocarboxylic acids Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters 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
- 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 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
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 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
- 238000002844 melting 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
- 239000000047 product Substances 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate 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
- 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
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
- D01F9/1271—Alkanes or cycloalkanes
- D01F9/1272—Methane
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
- D01F9/1273—Alkenes, alkynes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
- D01F9/133—Apparatus therefor
Abstract
Description
【発明の詳細な説明】
３、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 3. Detailed Description of the Invention (Field of Industrial Application) 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, the present invention relates to a method for producing carbon fibers. The present invention relates to a method for producing carbon fibers in which fibers are produced in a heated zone space.
（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
。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。(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. 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 vapor-grown carbon fiber has superior crystallinity and superior crystallinity compared to the former carbon fiber.
Because it has orientation, it is expected to be used in a wide variety of fields as a composite material that has both high strength and high elastic modulus.
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 involves spraying fine particles made of transition metals, as shown in, for example, "Kogyo Materials, July 1980 Issue, p. 109 (Endo, Koyama)". The fiber-generating 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 it, producing carbon fibers on the base material. be.
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とと
などから生産性が低いものであった。However, methods using such substrates have 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はいえなかった。On the other hand, JP-A-58-180615 describes a method in which ultrafine powder of a high-melting point metal or a compound of the metal is suspended in a hydrocarbon thermal decomposition zone. It has not been possible to find a method with excellent productivity because secondary particles are easily formed 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ヤガ
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太き（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が生
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 Japanese Unexamined Patent Publication 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 is much larger than the carbon source compound, and the yield is low. Further, according to the studies of the present inventors, the amount of raw materials supplied was increased in order to improve the production amount per hour (this resulted in problems such as a further decrease in the yield and the contamination of soot).
（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）
本発明は、炭素源化合物、触媒源化合物、キャリヤガス
および硫黄化合物とを加熱帯に供給して炭素繊維を製造
する方法において、加熱帯の温度を１３００°Ｃ以上お
よび単位時間当たりに加熱帯に供給するキャリヤガス量
（ｍｏｎ）を炭素源化合物の単位時間当たりの供給量（
ｇ）に対してＯｏＱ ４ ｍ ｏ （１／ ｇ以上とし
た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) 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 temperature of the heating zone is increased to 1300°. C or more and the amount of carrier gas (mon) supplied to the heating zone per unit time is calculated as the amount of carbon source compound supplied per unit time (mon).
This is a method for producing carbon fiber, characterized in that OoQ 4 m o (1/g or more) is set relative to g).
本発明における炭素源化合物とは、８００°Ｃ以上に加
熱することによって炭素を析出し得る化合物であり、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、ハロゲン等の誘導体、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 a compound that can precipitate carbon by heating to 800°C or higher, and covers carbon compounds in general. For example, CO, alkane compounds such as methane and ethane, alkene compounds such as ethylene and butadiene, alkyne compounds such as acetylene, aromatic compounds such as benzene, toluene, styrene, naphthalene and anthracene, cyclohexane, cyclopentadiene and dicyclopenta Examples include alicyclic hydrocarbon compounds such as Jen, derivatives thereof such as nitrogen, oxygen, halogen, etc., gasoline, kerosene, heavy oil, etc., and mixtures thereof may also be used.
加熱帯に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０．５ｇ／β・分以上が好ま
しく、特に１．０ｇ＃！・分以上、３０、０ ｇ ／
７！・分局下がより好ましい。供給量が少なすぎると煤
が混入する傾向があり、また多すぎると収率が低下して
煤も混入する傾向がある。The amount (g) of the carbon source compound supplied to the heating zone is preferably 0.5 g/β·min or more per minute per volume 11 of the heating zone, particularly 1.0 g#!・Minutes or more, 30.0 g/
7!・It is more preferable to use a branch office. If the amount supplied is too small, soot tends to be mixed in, while if it is too large, the yield tends to decrease and soot also tends to be mixed.
本発明における触媒源化合物としては、ＦｅＣｚ、、、
、Ｆｅ （Ｎｏ）４、ＮｉＣｌ２、Ｃｏ （ＮＯ）２
ＣＸ等の無機遷移金属化合物、Ｆｅ （Ｃ５Ｈ５）２、
Ｎｉ （Ｃ５Ｈｊ）２、Ｃｏ （Ｃｇ Ｈｇ）２、Ｆ
ｅ （Ｃｏ） ５、Ｆｅ２ （ＣＯ） １、Ｎｉ
（Ｃ０）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等が挙げられる。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６０−１８５８１８号、特開昭６（１−２２４８１
５号、特開昭６（１−２２４８１６号、特開昭６０−２
３１８２２号、特願昭５９−２３１９６７号、特願昭６
０−５８８１３号、特願昭６０−５８８１９号、特願昭
６０−１１３１０８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。Catalyst source compounds in the present invention include FeCz,...
, Fe (No)4, NiCl2, Co (NO)2
Inorganic transition metal compounds such as CX, Fe (C5H5)2,
Ni (C5Hj)2, Co (Cg Hg)2, F
e (Co) 5, Fe2 (CO) 1, Ni
Examples include organic transition metal compounds such as (C0)4, and transition metal compounds such as iron acetylacetonate, iron carboxylate, iron alkoxide, iron aryloxide, nickel thioalkoxide, cobalt alkoxide, and iron thioacetate. Two or more of these catalyst source compounds may be used simultaneously. Furthermore, as a catalyst source compound, JP-A-60-54998, JP-A-60-54999, JP-A-60-181319, JP-A-60-185818, JP-A-6 (1989-1-22481)
No. 5, Japanese Patent Application Publication No. 1-224816, Japanese Patent Application Publication No. 1986-2
No. 31822, Japanese Patent Application No. 59-231967, Japanese Patent Application No. 1983
Compounds described in Japanese Patent Application No. 0-58813, Japanese Patent Application No. 60-58819, Japanese Patent Application No. 113108-1982, Japanese Patent Application No. 123201-1982, etc. may be used.
加熱帯に供給する触媒源化合物の量（ｍｏｂ、）は、供
給する炭素源化合物の質量（ｇ）に対して、ｌＸ１０’
ｍｏＪ／ｇ以上、３ Ｘ １０−３ｍｏ Ｉｔ ７ｇ以
下が好ましく、特にｌＸｌ０−’ｍｏｌ／ｇ以上、Ｉ
Ｘ １０−３ｍｏ １．７ｇ以下がより好ましく用いら
れる。供給量が少なすぎると煤が混入する傾向があり、
多すぎると収率が低下する傾向がある。The amount (mob) of the catalyst source compound supplied to the heating zone is lX10' with respect to the mass (g) of the carbon source compound supplied.
moJ/g or more, 3 X 10-3mo It 7g or less is preferable, especially lXl0-'mol/g or more, I
1.7 g or less of X 10-3mo is more preferably used. If the supply is too low, it tends to be contaminated with soot;
If the amount is too large, the yield tends to decrease.
本発明におけるキャリヤガスとしては、Ｈ２ガス、Ｈｅ
ガス、Ｎ２ガス、Ｎｅガス、Ａｒガス、Ｋｒガス、ＣＯ
。ガス、ＮＨ３ガスを主体とするガスが挙げられ、これ
らの混合物を用いてもよい。As the carrier gas in the present invention, H2 gas, He
Gas, N2 gas, Ne gas, Ar gas, Kr gas, CO
. Examples include gases mainly composed of gas and NH3 gas, and mixtures thereof 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（ｍｏ７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ｏ、。In the present invention, the amount of carrier gas supplied to the heating zone per unit time (mo7 is o, relative to the amount of carbon source compound supplied per unit time (g)).
４ ｍ ｏ ７！／ ｇ以上である。キャリヤガス量が
０．０４ ｍ ｏ ｊ！ ／ ｇ未満では煤の得られる
割合が多くなる。キャリヤガス量は０．０４ ｍ ｏ
Ａ ／ ｇ以上、５゜９ ｍ ｏ １ ／ ｇ以下が好
ましく、特に０．０８ ｍ ｏ １７２以上、０．２５
ｍ ｏ ｎ！ ／ ｇ以下がより好ましい。4 m o 7! /g or more. Carrier gas amount is 0.04 m o j! /g, the proportion of soot obtained increases. Carrier gas amount is 0.04 m o
A/g or more and 5゜9 m o 1/g or less are preferable, particularly 0.08 m o 172 or more and 0.25 m o 1/g or less
m o n! /g or less is more preferable.
キャリヤガス量が多いと収率が低下する傾向がある。If the amount of carrier gas is large, the yield tends to decrease.
用いるキャリヤガスは、用いる炭素源化合物によっても
異なるが、３０ＶｏＩ！％以上を水素ガスとするのが好
ましく、特に５０ＶｏＪ％以上とするのが好ましい。水
素ガス量が少ないと煤が混入する傾向がある。The carrier gas used varies depending on the carbon source compound used, but is 30 VoI! % or more is preferably hydrogen gas, particularly preferably 50 VoJ% or more. If the amount of hydrogen gas is small, soot tends to get mixed in.
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挙げられ、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、エチル千オール、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、ジエチルジスルフィド、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
挙げられる。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, and organic sulfur compounds are particularly preferably used. Examples of organic sulfur compounds include thiols such as methylthiol, ethylthol, butylthiol, and phenylthiol; sulfides such as dimethyl sulfide, diethyl disulfide, and phenylmethyl sulfide; sulfoxides such as dimethyl sulfoxide, diethyl sulfoxide, and diphenyl sulfoxide; Sulfones such as dimethylsulfone 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 acids esters,
Thiol sulfinates, thiocarbonyl compounds, thiocarboxylic acids, thiocarboxylic acid esters, dithiocarboxylic acids, sulfines, thiocarboxylic acid derivatives S-
Examples include oxides, sulfonium ylides, and sulfurans. 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（ｍｏｂ）は、供給す
る炭素源化合物の質量（ｇ）に対して１×１０−’ｍｏ
４８７ｇ以上、ｌ ｘ １０−’ｍｏ １２／ｇ以下
が好ましく、特にｌＸｌ０−’ｍｏ７！／ｇｍ上７！Ｘ
１０−’ｍｏＪ／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 (mob) of the sulfur compound supplied to the heating zone is 1 × 10-'mo with respect to the mass (g) of the carbon source compound supplied.
487g or more and l x 10-'mo 12/g or less are preferable, especially lXl0-'mo7! /gm upper 7! X
More preferably, it is 10-'moJ/g or less. 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の温度は１３００℃以上であ９、
＋０ため６．−は反応ｉ器。内壁温度を１３００℃以上
に加熱する必要がある。１３００℃未満では加熱帯に供
給する原料（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）の量を多くすると収率が低下し、
また煤の混入も多くなってくる。内壁温度は１３００〜
２１００℃が好ましく、特に１３３０〜１９００℃がよ
り好ましい。内壁温度が高すぎると、煤の混、入牢が大
きくなる傾向がある。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、反応熱利用等の方法が挙
げられ、この中では電気炉加熱が便利である。The temperature of the heating zone in the present invention is 1300°C or higher9,
+0 for 6. - is reactor i. It is necessary to heat the inner wall temperature to 1300°C or higher. Below 1300°C, increasing the amount of raw materials (carbon source compound, catalyst source compound, carrier gas and sulfur compound) supplied to the heating zone will reduce the yield;
Also, more soot gets mixed in. Inner wall temperature is 1300~
The temperature is preferably 2100°C, and particularly preferably 1330 to 1900°C. If the inner wall temperature is too high, there is a tendency for soot to become mixed and trapped. The heating method is not particularly limited, but examples include methods such as electric furnace heating, infrared heating, plasma heating, laser heating, combustion heat utilization, and reaction heat utilization, among which 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。また、供給ノズル位置および温度
についても特に限定されない。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. Further, the supply nozzle position and temperature are not particularly limited either.
（発明の効果）
本発明方法によれば、煤のほとんど混入しない炭素繊維
を収率よく得ることができる。また、単位時間当たりの
生産性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, productivity per unit time can be greatly improved.
（実施例）
実施例１〜７、比較例１〜２
第１図に示すように、黒鉛ヒーターを有する電気炉１
（均熱帯の長さ８５ｃ＋ｎ）にモリブデン管２（内径６
０ｍ、長さ２ｆｎ）を設置し、モリブデン管２の一端に
ボックス３を接続した。そしてボックス３にフィルタ８
を設け、ボックス３から飛び出る繊維を収集できるよう
にした。またモリブデン管２の他の一端には原料を加熱
帯に供給するための導入バイブ４．５およびその先端に
導入ノズル６．７をそれぞれ設置した。(Example) Examples 1 to 7, Comparative Examples 1 to 2 As shown in FIG. 1, an electric furnace 1 having a graphite heater
(length of soaking zone 85c+n) and molybdenum pipe 2 (inner diameter 6
0 m, length 2fn) was installed, and a box 3 was connected to one end of the molybdenum pipe 2. and filter 8 in box 3
was installed to collect the fibers coming out of box 3. Further, at the other end of the molybdenum tube 2, an introduction vibrator 4.5 for supplying the raw material to the heating zone and an introduction nozzle 6.7 were installed at the tip thereof.
電気炉１内およびモリブデン管２内を窒素置換した後、
モリブデン管２の内壁温度を第１表に示した温度に設定
した。その後管内を水素ガスで置換し、導入バイブ５か
ら水素ガスを導入した。次にベンゼンに第１表に示すよ
うな供給量（８度）で触媒源化合物および硫黄化合物を
熔解させた溶液を、導入パイプ４から管内に噴出させた
。このヘンゼン溶液を５分間導入させた後、管内に水素
ガスのみをさらに５分間導入させた。これらの結果を第
１表に要約した。After replacing the inside of the electric furnace 1 and the molybdenum tube 2 with nitrogen,
The inner wall temperature of the molybdenum tube 2 was set to the temperature shown in Table 1. Thereafter, the inside of the tube was replaced with hydrogen gas, and hydrogen gas was introduced from the introduction vibrator 5. Next, a solution in which a catalyst source compound and a sulfur compound were dissolved in benzene at the feed rate (8 degrees) shown in Table 1 was jetted from the introduction pipe 4 into the pipe. After introducing this Hensen's solution for 5 minutes, only hydrogen gas was introduced into the tube for another 5 minutes. These results are summarized in Table 1.
以下余白
得られた炭素繊維は直径が０．２μ以下のものが多く、
また形態はストレートなものがほとんどであった。Many of the carbon fibers obtained have a diameter of 0.2μ or less,
Also, most of the shapes were straight.
実施例８．９
電気炉１ （均熱帯７０印）内に内径５０ｍｍのモリブ
デン管２を第２図に示したように設置した。Example 8.9 A molybdenum tube 2 having an inner diameter of 50 mm was installed in an electric furnace 1 (soaking zone marked 70) as shown in FIG.
電気炉１は、ヒーター１１の外側を断熱材１０で保温し
、ケーシング９で外装したものからなる。The electric furnace 1 consists of a heater 11 whose outside is insulated with a heat insulating material 10 and covered with a casing 9.
炭素源化合物としてトルエン、触媒源化合物としてフェ
ロセン、硫黄化合物としてチオフェンを用いた以外は実
施例１と同様に行なった。これらの結果を第２表に示し
た。The same procedure as in Example 1 was conducted except that toluene was used as the carbon source compound, ferrocene was used as the catalyst source compound, and thiophene was used as the sulfur compound. These results are shown in Table 2.
第 ２ 表Table 2
第１図および第２図は、それぞれ本発明の好ましい実施
態様の一例を示す炭素繊維製造装置の断面図である。
１・・・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・・・導入パイプ、６
．７・・・導入ノズル、８・・・フィルタ。FIG. 1 and FIG. 2 are sectional views of a carbon fiber manufacturing apparatus, each showing an example of a preferred embodiment of the present invention. DESCRIPTION OF SYMBOLS 1...Electric furnace, 2...Reaction container, 3...Box for storing products, 4.5...Introduction pipe, 6
．． 7...Introduction nozzle, 8...Filter.
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、加熱帯温度を１３００℃以上、単位時間当
たりに加熱帯に供給するキャリヤガス量（ｍｏｌ）を炭
素源化合物の単位時間当たりの供給量（ｇ）に対して０
．０４ｍｏｌ／ｇ以上とす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 gas is supplied to the heating zone per unit time to maintain the temperature of the heating zone at 1300°C or higher. The amount (mol) is 0 relative to the supply amount (g) of the carbon source compound per unit time.
．． A method for producing carbon fiber, characterized in that the carbon fiber content is 0.4 mol/g or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12078986A JPS62282020A (en) | 1986-05-26 | 1986-05-26 | Production of carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12078986A JPS62282020A (en) | 1986-05-26 | 1986-05-26 | Production of carbon fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62282020A true JPS62282020A (en) | 1987-12-07 |
Family
ID=14795038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12078986A Pending JPS62282020A (en) | 1986-05-26 | 1986-05-26 | Production of carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62282020A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5690997A (en) * | 1993-10-04 | 1997-11-25 | Sioux Manufacturing Corporation | Catalytic carbon--carbon deposition process |
| WO2005118473A1 (en) * | 2004-06-04 | 2005-12-15 | Japan Science And Technology Agency | Highly efficient process for producing carbon nanostructure through raw material blasting and apparatus tehrefor |
-
1986
- 1986-05-26 JP JP12078986A patent/JPS62282020A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5690997A (en) * | 1993-10-04 | 1997-11-25 | Sioux Manufacturing Corporation | Catalytic carbon--carbon deposition process |
| WO2005118473A1 (en) * | 2004-06-04 | 2005-12-15 | Japan Science And Technology Agency | Highly efficient process for producing carbon nanostructure through raw material blasting and apparatus tehrefor |
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