JPH0280619A - Production of carbon fiber - Google Patents
Production of carbon fiberInfo
- Publication number
- JPH0280619A JPH0280619A JP63228061A JP22806188A JPH0280619A JP H0280619 A JPH0280619 A JP H0280619A JP 63228061 A JP63228061 A JP 63228061A JP 22806188 A JP22806188 A JP 22806188A JP H0280619 A JPH0280619 A JP H0280619A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- carbon fibers
- carbon
- carbon fiber
- atmospheric 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.)
- Granted
Links
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 69
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 69
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims description 143
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 18
- 239000001569 carbon dioxide Substances 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 238000000354 decomposition reaction Methods 0.000 claims description 10
- 239000000571 coke Substances 0.000 claims description 9
- 150000002736 metal compounds Chemical class 0.000 claims description 9
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 16
- 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 abstract description 12
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 9
- 229910052742 iron Inorganic materials 0.000 abstract description 8
- 229930192474 thiophene Natural products 0.000 abstract description 6
- 239000010419 fine particle Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 150000003577 thiophenes Chemical class 0.000 abstract description 2
- 229910000765 intermetallic Inorganic materials 0.000 abstract 3
- 238000000197 pyrolysis Methods 0.000 abstract 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 44
- 238000000034 method Methods 0.000 description 23
- 229910002090 carbon oxide Inorganic materials 0.000 description 13
- 238000002485 combustion reaction Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 8
- -1 ferrocene Chemical class 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000000835 fiber Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000002309 gasification Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000002134 carbon nanofiber Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000004071 soot Substances 0.000 description 4
- 239000012808 vapor phase Substances 0.000 description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- FCEOGYWNOSBEPV-FDGPNNRMSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical class [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FCEOGYWNOSBEPV-FDGPNNRMSA-N 0.000 description 2
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical class [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000219112 Cucumis Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000003949 liquefied natural gas Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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
- 239000011882 ultra-fine particle Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene 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、気相法によりウィスカー状炭素繊維を製造す
る方法の改良に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an improvement in a method for producing whisker-like carbon fibers by a vapor phase method.
［従来技術］
炭素繊維には、気相法で得られる炭素繊維の他に、有機
繊維を焼成して製造されるＰＡＮ系炭素滋維やメソフェ
ーズピッチの溶融紡糸、不融化及び炭素化処理して製造
されるピッチ系炭素繊維等がある。気相法で得られる炭
素繊維は、他の繊維に比べて、引張り強度が高いなど機
械的特性に優れ、また電気的伝導性、熱伝導性にも優れ
ている。[Prior art] In addition to carbon fiber obtained by the vapor phase method, carbon fibers include PAN-based carbon fibers produced by firing organic fibers and mesophase pitch melt-spun, infusible and carbonized. There are pitch-based carbon fibers that are produced. Carbon fiber obtained by the vapor phase method has excellent mechanical properties such as high tensile strength compared to other fibers, and also has excellent electrical conductivity and thermal conductivity.
このため近時機能性材料として特に注目を浴びている。For this reason, it has recently attracted particular attention as a functional material.
例えば、２８００℃で黒鉛化処理した気相法炭素繊維は
、引張り強度が７００ｋｇ／ｍｍ２引張り弾性率が７０
ｔｏｎ／ｍｍ２と極めて高い値である。これらの優れた
諸特性は、炭素繊維の結晶配向性の高さに基づくものと
考えられている。For example, vapor grown carbon fiber graphitized at 2800°C has a tensile strength of 700 kg/mm2 and a tensile modulus of 70.
This is an extremely high value of ton/mm2. These excellent properties are thought to be based on the high crystal orientation of carbon fibers.
気相法炭素繊維は、上記特性を有するため、その利用分
野は幅広く、例えば、ＦＲＰＳＦＲＭ。Since the vapor-grown carbon fiber has the above-mentioned characteristics, it can be used in a wide range of fields, such as FRPS FRM.
ＦＲセメント、Ｃ／Ｃコンポジット等、種々の複合材料
の繊維補強材料として利用されている。これらは、宇宙
、航空産業、自動車産業、建設、電気産業など、多くの
産業に適用しうる素材であり、この炭素繊維への期待は
非常に大きい。また最近では、精密機械のＯＡ化、ＦＡ
化への利用により電磁遮蔽材料の要請が高まり、良質な
炭素繊維が望まれている。さらにまたこの炭素繊維は、
黒鉛層間化合物に容易に変換することができるが、この
ものは銅線に代わる伝導材料として注目されている。It is used as a fiber reinforcing material for various composite materials such as FR cement and C/C composites. These are materials that can be applied to many industries, including the space, aviation, automobile, construction, and electrical industries, and there are great expectations for carbon fibers. In addition, recently, OA of precision machinery, FA
The demand for electromagnetic shielding materials is increasing due to the use of carbon fibers, and high-quality carbon fibers are desired. Furthermore, this carbon fiber
It can be easily converted into a graphite intercalation compound, which is attracting attention as a conductive material that can replace copper wire.
あった。これを克服するために、流動床方式により、触
媒である超微粒子金属を反応器内に浮遊させてこれに炭
素を成長させる流動床方式が開発された（特開昭５７−
５８９６６号参照）。この方式は、反応器内の空間を三
次元的に利用するため、原理的に収率高く、連続生産が
可能である。このため、気相法炭素繊維の製造方法の主
流となっている。there were. In order to overcome this problem, a fluidized bed method was developed in which ultrafine metal particles as a catalyst are suspended in a reactor and carbon is grown thereon.
58966). This method uses the space inside the reactor three-dimensionally, so in principle, the yield is high and continuous production is possible. For this reason, this method has become the mainstream method for producing vapor-grown carbon fibers.
しかしながら、工業的規模で生産する場合には、まだい
くつかの課題がある。However, there are still some challenges when producing on an industrial scale.
第１の課題は、炭素繊維の成長速度が、固定床法に比べ
て高いというものの、工業規模で生産するのに、かなら
ずしも十分満足できる成長速度ではなく、その収率が十
分高いとは言えないということである。この技術では、
フェロセンなどの有機化合物を熱分解させて、炭素繊維
成長用の超微粒触媒を生成しているが、有機金属化合物
の熱分解が複雑なため、その鉄原子としての利用率が極
めて低く、触媒として作用する３００Å以下の粒径を有
する超微粒を選択的に生成することは非常に困難である
。しかし、一般に炭素繊維の成長速度は、触媒の粒径が
小さい程高く、その収率は３００Å以下の粒径を有する
超微粒の量が多い程高いと考えられている。したがって
、例えば、特開昭６０−５４９９８号では、触媒となる
フェロセンは炭素繊維となるベンゼンに対して２．５倍
量も用いている。このような方法では、有機金属化合物
の製品に占めるコストは高い。The first problem is that although the growth rate of carbon fiber is higher than that of the fixed bed method, the growth rate is not necessarily sufficient for production on an industrial scale, and the yield cannot be said to be high enough. That's what it means. With this technology,
Ultrafine catalysts for carbon fiber growth are produced by thermally decomposing organic compounds such as ferrocene, but because the thermal decomposition of organometallic compounds is complicated, their utilization rate as iron atoms is extremely low, making them difficult to use as catalysts. It is very difficult to selectively produce ultrafine grains with a grain size of 300 Å or less. However, it is generally believed that the growth rate of carbon fibers increases as the particle size of the catalyst becomes smaller, and the yield increases as the amount of ultrafine particles having a particle size of 300 Å or less increases. Therefore, for example, in JP-A-60-54998, the amount of ferrocene used as a catalyst is 2.5 times that of benzene used as carbon fiber. In such a method, the cost of the organometallic compound product is high.
第２の課題は、雰囲気ガス源である。流動床方式による
製造方法の改良として、特開昭６０−５４９８号、特開
昭６０−２２４８１５号、特開昭６１−１０８７２３号
へ特開昭６１−２２５３２８号などが提案されているが
、これらの方法では雰囲気ガスは、いずれも水素ガスを
主体とするものである。しかし、水素ガスを使用して炭
素繊維を高い収率で得るためには、水素ガスが８０％以
上の純度の水素ガスが必要と考えられている。また許容
されるガス中の不純物としては、窒素などの不活性ガス
に限られ、水分や酸素などは触媒を不活性化させ、好ま
しくはない。The second issue is the source of atmospheric gas. As improvements to the production method using the fluidized bed method, JP-A-60-5498, JP-A-60-224815, JP-A-61-108723, and JP-A-61-225328 have been proposed. In both methods, the atmospheric gas is mainly hydrogen gas. However, in order to obtain carbon fibers at a high yield using hydrogen gas, it is thought that hydrogen gas must have a purity of 80% or more. In addition, allowable impurities in the gas are limited to inert gases such as nitrogen, and moisture, oxygen, etc. are not preferred because they inactivate the catalyst.
さらに高濃度の炭化水素ガスが混入する場合、その加熱
により熱分解してススが生成する。この結果、製品の純
度を下げ、好ましくはない。また雰囲気ガスは、一般に
原料の炭化水素に対し、−倍容量以上必要であり、工業
規模で生産する場合、膨大なガス瓜を必要とする。高価
な水素を使用する場合、その再利用をする必要があり、
そのための精製装置が必要となり、極めて経済性が低く
なる欠点がある。Furthermore, if a high concentration of hydrocarbon gas is mixed in, it will be thermally decomposed by heating and soot will be produced. This results in a decrease in the purity of the product, which is undesirable. In addition, the atmospheric gas generally needs to be more than twice as large in volume as the raw material hydrocarbon, and when produced on an industrial scale, a huge amount of gas melon is required. When using expensive hydrogen, it is necessary to reuse it.
A refining device is required for this purpose, which has the drawback of extremely low economic efficiency.
従来の雰囲気ガスである水素は、触媒である超微粒鉄の
還元、表面の清浄化、生成した炭素のガス化などである
と考えられている。そこで本発明者は、水素の代替とし
て一酸化炭素を雰囲気ガスとして選択し、検討したとこ
ろ、転炉ガスが利用可能であり、また転炉ガス中に含ま
れる微粒子のダストが触媒能を有すること、熱源として
排熱を利用できることなどを見出だし、高温の転炉ガス
を雰囲気ガスとして直接利用する発明について特許出願
した（特開昭６３−０１２７０号参照）。Hydrogen, which is a conventional atmospheric gas, is thought to be used to reduce the ultrafine iron catalyst, clean the surface, and gasify the generated carbon. Therefore, the present inventor selected carbon monoxide as an atmospheric gas as a substitute for hydrogen, and after considering it, it was found that converter gas can be used and that the fine particle dust contained in converter gas has catalytic ability. discovered that exhaust heat could be used as a heat source, and filed a patent application for an invention for directly using high-temperature converter gas as atmospheric gas (see Japanese Patent Laid-Open No. 63-01270).
この転炉ガスは、高炉で製造された溶銑から酸素により
炭素、珪素などの成分調整し、鋼を製造する過程で発生
するガスで、これまで鉄鋼業においてせいぜい燃料とし
て用いられているにすぎず、その組成は、操業条件によ
り異なるが、おおよそ−酸化炭素６０〜８０％、二酸化
炭素１０〜２０％、窒素５〜２０％、水素０．５〜２％
、酸素１．０％以下である。This converter gas is a gas generated during the process of manufacturing steel by adjusting the composition of carbon, silicon, etc. from hot metal produced in a blast furnace with oxygen, and has so far been used at most as a fuel in the steel industry. , its composition varies depending on operating conditions, but approximately - 60-80% carbon oxide, 10-20% carbon dioxide, 5-20% nitrogen, 0.5-2% hydrogen.
, oxygen content is 1.0% or less.
しかし、この方法では、転炉ガスをそのまま使用するの
で、転炉の操業初期、終期のガス変動や高温転炉ガス中
に含まれる粗粒ダストの分離が困難である。しかも炭素
繊維の収率が満足できる程度高いとはいえず、品質にも
バラツキがあるなどの問題があった。However, in this method, since the converter gas is used as it is, it is difficult to separate the gas fluctuations at the beginning and end of the operation of the converter and the coarse dust contained in the high-temperature converter gas. Furthermore, there were problems such as the yield of carbon fibers being not satisfactorily high and the quality being inconsistent.
第３の課題は、熱源の問題である。気相法によるもので
は、１０００℃以上の高温が必要であり、工業規模で生
産する場合、そのエネルギーは膨大なものであり、その
加熱方式として電気炉は経済的には採用できない。燃料
の燃焼排ガスによる内部加熱方式も考えられるが、この
場合、燃焼排ガス中に水分やススが含まれてしまい、炭
素繊維の生成が妨げられるという欠点がある。The third issue is the issue of heat sources. The gas phase method requires a high temperature of 1000° C. or higher, and when produced on an industrial scale, the energy required is enormous, and an electric furnace cannot be economically employed as a heating method. An internal heating method using fuel combustion exhaust gas is also considered, but in this case, the combustion exhaust gas contains moisture and soot, which hinders the production of carbon fibers.
第４の課題は、表面修飾の問題である。一般に気相法で
得られる炭素繊維は、黒鉛結晶が年輪状かかる欠点があ
る。The fourth issue is the problem of surface modification. Generally, carbon fibers obtained by the vapor phase method have the disadvantage that graphite crystals form in the form of tree rings.
［課題を解決するための手段］
本発明者は、かかる課題を解決するために鋭意検討した
結果、有機金属化合物の分解触媒として金属化合物を添
加することにより、有機金属化合物の熱分解で生成され
る炭素繊維成長用微細金属粒子に３００Å以下の粒径の
ものが多く含まれるようにして、炭素繊維の成長速度に
関する第１の課題を解決した。[Means for Solving the Problems] As a result of intensive studies to solve the problems, the present inventors have discovered that by adding a metal compound as a decomposition catalyst of the organometallic compound, the metal compound produced by the thermal decomposition of the organometallic compound can be reduced. The first problem regarding the growth rate of carbon fibers was solved by making the fine metal particles for carbon fiber growth contain many particles with a particle size of 300 Å or less.
また雰囲気ガスとして転炉ガスなど一酸化炭素５０〜８
０％と二酸化炭素５〜３０％とを少な（とも含むガスを
利用し、この雰囲欠ガスを直接反応容器内に高温のまま
導入することなく、−旦ガスホルダー内に貯蔵しておき
、ガスホルダーからのガスの加熱を少なくとも２つの熱
風炉で交互におこなうことにより、雰囲気ガスに関する
第２の課題及び熱源に関する第３の課題を解決した。In addition, as atmospheric gas, carbon monoxide such as converter gas is 50 to 8
Using a gas containing a small amount of both 0% and 5 to 30% carbon dioxide, this atmospheric gas is stored in a gas holder without directly introducing it into the reaction vessel at high temperature, The second problem related to the atmospheric gas and the third problem related to the heat source were solved by alternately heating the gas from the gas holder using at least two hot air stoves.
さらに上記組成の雰囲気ガスを使用することにより、雰
囲気ガスがキャリアガスとしての機能のみならず、二酸
化炭素が炭素のガス化作用を成して炭素繊維の表面修飾
をなし、−酸化炭素が表面修飾された炭素繊維表面上に
炭素析出せしめる機能を有し、このことにより、表面修
飾に関する第４の課題を解決するものである。Furthermore, by using an atmospheric gas having the above composition, the atmospheric gas not only functions as a carrier gas, but also carbon dioxide gasifies carbon and modifies the surface of carbon fibers, and carbon oxide modifies the surface. It has a function of causing carbon to be deposited on the surface of carbon fibers, thereby solving the fourth problem regarding surface modification.
以下、本発明を具体的に説明する。The present invention will be specifically explained below.
本発明は、反応容器内に炭化水素（原料炭素源）と有機
金属化合物を導入し、炭化水素の熱分解で得られた炭素
を、有機金属化合物の熱分解で生成された微粒子上に成
長させる方法において、前記反応容器内に前記有機金属
化合物の分解触媒として金属化合物を導入する方法であ
る。The present invention introduces a hydrocarbon (raw carbon source) and an organometallic compound into a reaction vessel, and grows carbon obtained by thermal decomposition of the hydrocarbon on fine particles generated by thermal decomposition of the organometallic compound. In this method, a metal compound is introduced into the reaction vessel as a decomposition catalyst for the organometallic compound.
本発明で使用する炭化水素には、メ、タン、エタン、プ
ロパン、エチレン、プロピレン、フタジエン等の脂肪族
炭化水素、ベンゼン、トルエン、キシレン、などの単環
芳香族炭化水素をはじめ、ナフタレン、アントラセンな
どの多環芳香族炭化水素、あるいはこれらの混合物を適
用できるが、コークス炉からの副生物である粗軽油類、
吸収油、カルポル浦、アントラセン油、重油、ピッチ、
およびこれらの混合物は、安価で大量に供給が可能であ
り、特に硫黄を含むチオフェン類、チオール類、および
チオフェノール類は炭素繊維の生成速度が速くなり有用
である。The hydrocarbons used in the present invention include aliphatic hydrocarbons such as methane, ethane, propane, ethylene, propylene, and phthalene, monocyclic aromatic hydrocarbons such as benzene, toluene, and xylene, naphthalene, and anthracene. Polycyclic aromatic hydrocarbons, such as polycyclic aromatic hydrocarbons, or mixtures thereof can be applied, but crude light oils, which are by-products from coke ovens,
Absorption oil, Calpolura, anthracene oil, heavy oil, pitch,
These mixtures can be supplied in large quantities at low cost, and sulfur-containing thiophenes, thiols, and thiophenols are particularly useful because they increase the rate of carbon fiber production.
有機金属化合物は、炭素−金属結合を有するものであれ
ば公知のものをいずれも使用可能であるが、原料炭化水
素に溶解して用いる場合は溶解性のあるもの、ガス状で
用いる場合は昇華性のあるものが望ましい。具体的には
、チタン、バナジウム、クロム、マンガン、鉄、コバル
ト、ニッケル、ルビジウム、ロジウム、タングステン、
パラジウムを含有する有機遷移金属化合物であり、その
うち特に鉄、ニッケル、コバルトを含有する有機金属化
合物が好適であり、鉄を含有する有機金属化合物が最も
好ましい。Any known organometallic compound can be used as long as it has a carbon-metal bond, but if it is used by dissolving it in the raw material hydrocarbon, it should be soluble, and if it is used in a gaseous state, it should be sublimated. Something with gender is desirable. Specifically, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, rubidium, rhodium, tungsten,
Organic transition metal compounds containing palladium, among which organometallic compounds containing iron, nickel, and cobalt are particularly preferred, and organometallic compounds containing iron are most preferred.
何機金属化合物の分解触媒である金属化合物は、有機金
属化合物を分解して３００Å以下の炭素繊維成長用金属
微粒子を多く生成するために添加する。金属化合物は、
使用する有機金属化合物１モルに対し、０．０１〜５０
モル程度加えればよい。The metal compound which is a decomposition catalyst for the organic metal compound is added in order to decompose the organometallic compound and produce many metal fine particles for carbon fiber growth of 300 Å or less. Metal compounds are
0.01 to 50 per mole of organometallic compound used
Just add about mol.
また、遷移金属化合物は、使用する有機金属化合物に対
して同種あるいは異種の金属原子を有するものであれば
いずれの錯体にも利用できる。その金属としては、チタ
ン、バナジウム、クロム、モリブデン、タングステン、
マンガン、鉄、コバルト、ニッケル、ルテニウム、ロジ
ウム、オスニウム、イリジウムが好ましく、マンガン、
鉄、コバルト、ニッケルが特に好ましい。化合物の形態
は、いずれでもよく、例えば硫酸塩、硝酸塩、酢酸塩、
塩化物、硫化物、酸化物、炭化物、窒化物、アセチルア
セトナート塩など無機化合物およびカルボニル化合物な
どの有機遷移金属錯体などが用いられる。Further, the transition metal compound can be used in any complex as long as it has metal atoms of the same type or different type with respect to the organometallic compound used. The metals include titanium, vanadium, chromium, molybdenum, tungsten,
Manganese, iron, cobalt, nickel, ruthenium, rhodium, osmium, and iridium are preferred, and manganese,
Particularly preferred are iron, cobalt and nickel. The compound may be in any form, such as sulfate, nitrate, acetate,
Inorganic compounds such as chlorides, sulfides, oxides, carbides, nitrides, acetylacetonate salts, and organic transition metal complexes such as carbonyl compounds are used.
本発明では、−酸化炭素５０〜８０％と二酸化炭素５〜
３０％とを少なくとも含むガスを雰囲気ガスとして使用
し、とくに容積比で、−酸化炭素１部に対し、二酸化炭
素０．０６〜０．６、水素０．００１〜０．２を含む組
成が好ましい。−酸化炭素、二酸化炭素及び水素の組成
範囲を限定した理由は、二酸化炭素、水素の炭素繊維の
ガス化作用と一酸化炭素の炭素析出作用との兼合いで設
定されたもので、これらの範囲から外れると各ガスのバ
ランスが崩れ、以下に示す所望の炭素繊維を得ることが
できないためである。この雰囲気ガスは、具体的には、
転炉ガス、高炉ガス、これらの混合ガス、これらのガス
にコークス炉ガス等の水素含有ガスを混合したガスであ
る。ただし、転炉ガス単独の組成でも、上記組成を満足
することができ、好適である。本発明では、この雰囲気
ガスを予め加熱して反応帯域である６００〜１３００℃
に保持する際に、高炉などで使用されている熱風炉方式
を採用する方法をおこなう。すなわち、転炉ガス等を高
温のまま直接反応容器内に導入することなく、−旦ガス
ホルダー内に貯蔵し、ガスホルダーからのガスを加熱炉
で加熱する。In the present invention, -50 to 80% of carbon oxide and 5 to 80% of carbon dioxide
A gas containing at least 30% of carbon dioxide is used as the atmospheric gas, and a composition containing 0.06 to 0.6 of carbon dioxide and 0.001 to 0.2 of hydrogen per 1 part of -carbon oxide in volume ratio is particularly preferred. . - The reason for limiting the composition ranges of carbon oxide, carbon dioxide, and hydrogen was to balance the gasification action of carbon dioxide and hydrogen with the carbon fiber action and the carbon precipitation action of carbon monoxide. This is because if it deviates from the above, the balance of each gas will collapse, making it impossible to obtain the desired carbon fiber shown below. Specifically, this atmospheric gas is
These include converter gas, blast furnace gas, mixed gases thereof, and gases obtained by mixing these gases with hydrogen-containing gas such as coke oven gas. However, the composition of the converter gas alone can satisfy the above composition and is suitable. In the present invention, this atmospheric gas is heated in advance to 600 to 1300°C, which is the reaction zone.
To maintain the temperature in a hot stove, a hot blast furnace method used in blast furnaces and the like is used. That is, the converter gas or the like is not directly introduced into the reaction vessel at high temperature, but is first stored in a gas holder, and the gas from the gas holder is heated in a heating furnace.
この方法によれば、粗粒ダストが除去され、しかもガス
ホルダーからガス組成の安定した転炉ガス等の利用を図
れる。本発明では、少なくとも二つの熱風炉（蓄熱炉）
を反応容器と接続している。According to this method, coarse grain dust is removed and, moreover, converter gas or the like having a stable gas composition can be used from the gas holder. In the present invention, at least two hot blast furnaces (heat storage furnaces)
is connected to the reaction vessel.
熱風炉では、燃焼用ガスを燃焼させ炉内に充填された充
填物を１０００〜１６００℃に加熱し、その後熱風炉か
ら反応器に導入される雰囲気ガスの温度が６００〜１３
００℃になるように雰囲気ガスを加熱、導入する。この
時、燃焼排ガス中に含まれる水分やススは燃焼排ガスを
雰囲気ガスで置換することにより可能である。また、熱
風炉を少なくとも二基備えているので、燃焼、燃焼排ガ
ス置換、雰囲気ガス流通のサイクルが可能となり、連続
して６００〜１３００℃に加熱された雰囲気ガスを反応
容器に導入することができる。ここで本発明で使用する
燃料用ガスは、水素、プロパン、ナフサ、ＬＮＧ、石油
ガス、その混合物、製鉄所で発生する高炉ガス、転炉ガ
ス、コークス炉ガス、およびその混合物が使用可能であ
るが、特に水、ススの発生を抑制するために高炉ガス、
転炉ガス、コークス炉ガス、及びその混合物が有用であ
る。In a hot blast furnace, the combustion gas is combusted and the filling filled in the furnace is heated to 1000-1600°C, and then the temperature of the atmospheric gas introduced from the hot blast furnace into the reactor is 600-130°C.
Atmosphere gas is heated and introduced to a temperature of 00°C. At this time, moisture and soot contained in the combustion exhaust gas can be removed by replacing the combustion exhaust gas with atmospheric gas. In addition, since it is equipped with at least two hot air stoves, a cycle of combustion, combustion exhaust gas replacement, and atmospheric gas distribution is possible, and atmospheric gas heated to 600 to 1300°C can be continuously introduced into the reaction vessel. . Here, as the fuel gas used in the present invention, hydrogen, propane, naphtha, LNG, petroleum gas, mixtures thereof, blast furnace gas generated in steel plants, converter gas, coke oven gas, and mixtures thereof can be used. However, in order to suppress the generation of water and soot, blast furnace gas,
Converter gas, coke oven gas, and mixtures thereof are useful.
また燃料用ガスの燃焼には、公知の方法を適用すること
ができる。バーナーも各種任意に使用することができる
。使用される充填物は、１６００℃程度の高温にて安定
であれば、任意のものを使用することができる。特にセ
ラミックペブルなどが望ましい。Further, a known method can be applied to combustion of the fuel gas. Any burner can also be used. Any filler can be used as long as it is stable at a high temperature of about 1600°C. Ceramic pebbles are particularly desirable.
このような条件下で炭素繊維を成長させると、炭素′ａ
維の表面が凹凸状のものが得られる。このような性状は
、高温の転炉排ガスを反応容器内に直接導入した方法で
は認められない。本発明者は、雰囲気ガスに含まれる一
酸化炭素が炭素繊維上への炭素析出に寄与し、一方二酸
化炭素が炭素のガス化に寄与して表面をサイジングする
と考えている。すなわち二酸化炭素は、炭素の構造に対
してガス化速度が敏感であり、例えば黒鉛に対する木炭
のガス化速度は１００００倍になるとも言われている。When carbon fiber is grown under such conditions, carbon'a
The surface of the fiber is uneven. Such properties are not observed in methods in which high-temperature converter exhaust gas is directly introduced into the reaction vessel. The present inventor believes that carbon monoxide contained in the atmospheric gas contributes to carbon deposition on the carbon fibers, while carbon dioxide contributes to gasification of carbon and sizing the surface. That is, the gasification rate of carbon dioxide is sensitive to the structure of carbon, and it is said that, for example, the gasification rate of charcoal is 10,000 times that of graphite.
従って、表面に存在する非結晶性の炭素に対するガス化
速度が結晶性の炭素に対する場合よりも速く、炭素繊維
表面上に複合材用補強繊維として極めて有用な凹凸を持
った結晶性の炭素繊維を作り出すことが可能である。ま
た−酸化炭素は、その不均化反応により炭素を析出する
ことが知られており、その熱分解炭素により凹凸を持っ
た結晶性の炭素繊維表面に、更に凹凸上に炭素を沈積せ
しめることができる。これに対して従来雰囲気ガスとし
て使用していた水素では、得られる炭素繊維は、平滑で
あり、その繊維径も極めて小さい。本発明で一酸化炭素
及び二酸化炭素の組成範囲を上記のように限定した理由
は、上記範囲から外れると所望の炭素繊維を得ることが
困難となるためである。Therefore, the gasification rate of amorphous carbon existing on the surface is faster than that of crystalline carbon, and crystalline carbon fibers with irregularities on the carbon fiber surface are extremely useful as reinforcing fibers for composite materials. It is possible to create. Furthermore, carbon oxide is known to precipitate carbon through its disproportionation reaction, and the pyrolytic carbon can cause carbon to be deposited on the uneven surface of crystalline carbon fibers. can. On the other hand, when using hydrogen, which has conventionally been used as an atmospheric gas, the obtained carbon fibers are smooth and have an extremely small fiber diameter. The reason why the compositional ranges of carbon monoxide and carbon dioxide are limited as described above in the present invention is that it becomes difficult to obtain desired carbon fibers outside the above ranges.
［発明の効果］
本発明によれば、有機金属化合物の分解触媒として金属
化合物を添加したので、有機金属化合物の熱分解で生じ
る金属微細粒子の粒径の多くを３００Å以下とすること
ができ、この結果、炭素繊維の成長速度を著しく高め、
工業規模での生産を可能とした。また−酸化炭素と二酸
化炭素を含むガスを雰囲気ガスとしたので、雰囲気ガス
が単にキャリアガスとしの機能だけでなく、炭素繊維の
表面修飾する機能を有し、得られる炭素繊維の特性を優
れたものとすることができる。またこの雰囲気ガスは、
熱風炉で加熱する方式であるため、ガスの性状の問題、
熱源の問題を解決し、良好な品質の炭素繊維を安定して
製造することができる。[Effects of the Invention] According to the present invention, since a metal compound is added as a decomposition catalyst for an organometallic compound, most of the particle diameters of metal fine particles generated by thermal decomposition of an organometallic compound can be reduced to 300 Å or less, As a result, the growth rate of carbon fiber is significantly increased,
This enabled production on an industrial scale. In addition, since the atmospheric gas was a gas containing carbon oxide and carbon dioxide, the atmospheric gas not only functions as a carrier gas, but also has the function of modifying the surface of carbon fibers, improving the properties of the resulting carbon fibers. can be taken as a thing. Also, this atmospheric gas is
Because it is heated using a hot air stove, there are problems with the properties of the gas.
It solves the heat source problem and allows stable production of high quality carbon fiber.
［実施例］ 以下に本発明を実施例にて説明する。[Example] The present invention will be explained below with reference to Examples.
実施例１
第１図に示す装置を使用して、炭素繊維を製造した。図
中、参照符号１１は、アルゴンガスを充填したガスボン
ベである。１２は、転炉ガスを充填したガスボンベで、
転炉ガスは一酸化炭素ガスフ０容量％、二酸化炭素ガス
１５容量％、水素ガス１．１容量％、窒素ガス１５容量
％の組成のガスであり、これを反応容器内に雰囲気ガス
として導入する。各ボンベ１１．１２には、流量計１３
゜１４がそれぞれ接続され、これによりガス流量を制御
している。１５は原料タンクで、ここには原料油として
、ベンゼンをいれた。このベンゼン内には、フェロセン
とチオフェンとフェロセンの分解触媒であるＭｎ（ＩＩ
）アセチルアセトナート塩が溶解され、その重量組成比
は、ベンゼン１００ｆｆｉ［部に対して、フェロセン、
チオフェン、Ｍｎ（ＩＩ）アセチルアセトナート塩が、
それぞれ０．４．０．２．０．１の割合である。これら
ボンベ１１．１２は、ステンレス製のバイブ１６を介し
て反応管２０に接続され、また原料タンク１５は、ステ
ンレス製のバイブ１７を介して反応管２０（反応容器）
と接続されている。反応管２０は、内径９０ｍｍ、長さ
１０００ｍｍのアルミナ管であり、その長さ８００ｍｍ
に亙って外周に電気炉２３が設置されている。この電気
炉２３の温度は、熱電対２４で検知し、温度制御器２５
で一定温度に制御している。この実施例では、電気炉２
３の運転中の温度は、１１５０℃に設定した。Example 1 Carbon fibers were manufactured using the apparatus shown in FIG. In the figure, reference numeral 11 is a gas cylinder filled with argon gas. 12 is a gas cylinder filled with converter gas,
The converter gas has a composition of 0% by volume of carbon monoxide gas, 15% by volume of carbon dioxide gas, 1.1% by volume of hydrogen gas, and 15% by volume of nitrogen gas, and is introduced into the reaction vessel as an atmospheric gas. . Each cylinder 11.12 has a flow meter 13
14 are connected to each other, thereby controlling the gas flow rate. 15 is a raw material tank, in which benzene was put as raw material oil. This benzene contains Mn(II), which is a decomposition catalyst for ferrocene, thiophene, and ferrocene.
) Acetylacetonate salt is dissolved, and the weight composition ratio is 100ffi [parts of benzene, ferrocene,
Thiophene, Mn(II) acetylacetonate salt,
The ratio is 0.4.0.2.0.1, respectively. These cylinders 11 and 12 are connected to the reaction tube 20 via a stainless steel vibrator 16, and the raw material tank 15 is connected to the reaction tube 20 (reaction vessel) via a stainless steel vibrator 17.
is connected to. The reaction tube 20 is an alumina tube with an inner diameter of 90 mm and a length of 1000 mm, and its length is 800 mm.
An electric furnace 23 is installed around the outer periphery. The temperature of this electric furnace 23 is detected by a thermocouple 24, and is detected by a temperature controller 25.
The temperature is controlled at a constant temperature. In this embodiment, electric furnace 2
The temperature during operation of No. 3 was set at 1150°C.
運転に際し、まず、ボンベ１１からアルゴンガスを反応
管内に供給し、反応管内をアルゴンガスで置換しておく
。続いてボンベ１２に収容した転炉ガスを３００ｍ１／
分で反応管２０内に流した。During operation, first, argon gas is supplied from the cylinder 11 into the reaction tube, and the inside of the reaction tube is replaced with argon gas. Next, converter gas contained in cylinder 12 was pumped to 300 m1/
The mixture was allowed to flow into the reaction tube 20 within minutes.
更に、上記原料油をケミカルポンプ２２を使って２ｍ１
／分の割合で反応管２０内に供給した。反応管内におい
て、原料油の熱分解および触媒反応が生じ、これによっ
て連続的にウィスカー状炭素繊維が生成され、これを捕
集器２１で捕集した。Furthermore, the above raw material oil is pumped to 2ml using the chemical pump 22.
was supplied into the reaction tube 20 at a rate of 1/min. In the reaction tube, thermal decomposition and catalytic reaction of the raw material oil occurred, thereby continuously producing whisker-like carbon fibers, which were collected by the collector 21.
得られた炭素繊維は、平均径が１μｍ１平均長さが２０
００μｍであり、透過電子顕微鏡により観察の結果、表
面が粗く、毛羽立つ様相を呈していた。収率はベンゼン
に対して６８％であった。The obtained carbon fibers have an average diameter of 1 μm and an average length of 20 μm.
00 μm, and as a result of observation using a transmission electron microscope, the surface was rough and had a fluffy appearance. The yield was 68% based on benzene.
実施例２
フェロセンの分解触媒として、実施例１で使用したＭｎ
（ＩＩ）アセチルアセトナート塩の代わりに、コバルト
（ＩＩ）アセチルアセトナート塩を使用し、それ以外、
実施例１と同様の条件で実施した。その結果、得られた
炭素繊維は、平均径が１μｍ１平均長さが３０００μｍ
であり、透過電子顕微鏡による観察の結果、実施例１と
同様に、表面が粗く、毛羽立つ様相を呈していた。収率
はベンゼンに対して７０％と高い値を示した。Example 2 Mn used in Example 1 as a ferrocene decomposition catalyst
(II) cobalt (II) acetylacetonate salt is used instead of acetylacetonate salt; otherwise,
It was carried out under the same conditions as in Example 1. As a result, the obtained carbon fibers had an average diameter of 1 μm and an average length of 3000 μm.
As a result of observation using a transmission electron microscope, the surface was found to be rough and fluffy, as in Example 1. The yield was as high as 70% based on benzene.
実施例３
実施例１と同様の装置を使用したが、ボンベ１２には、
−酸化炭素ガスを主体とした雰囲気ガスを充填した。こ
の雰囲気ガス組成は、−酸化炭素ガスフ６容量％、二酸
化炭素ガス１９容量％、水素ガス２．８容量％、メタン
ガス１．５容量％、残部窒素ガスである。そして実施例
と同じ条件で実施した結果、得られた炭素繊維は、平均
径が１μｍ１平均長さが３０００μｍであり、透過電子
顕微鏡による観察の結果、表面が粗く、毛羽立つ様相を
呈していた。収率はベンゼンに対して７０％と高い値を
示した。Example 3 The same equipment as in Example 1 was used, but the cylinder 12 was
- Filled with an atmosphere gas mainly composed of carbon oxide gas. The atmospheric gas composition is -carbon oxide gas 6% by volume, carbon dioxide gas 19% by volume, hydrogen gas 2.8% by volume, methane gas 1.5% by volume, and the remainder nitrogen gas. The carbon fibers obtained under the same conditions as in the examples had an average diameter of 1 μm and an average length of 3000 μm, and as a result of observation using a transmission electron microscope, the surface was rough and had a fluffy appearance. The yield was as high as 70% based on benzene.
実施例４
実施例１と同様の装置を使用したが、ボンベ１２には、
−酸化炭素ガスを主体とした雰囲気ガスを充填した。こ
の雰囲気ガス組成は、転炉ガス９７容量％と、コークス
炉ガス３容量％との混合ガスを用い、その組成は、−酸
化炭素ガス６８容量％、二酸化炭素ガス１３容量％、水
素ガス４．０容量％、メタンガス１．０容量％、窒素ガ
ス１４容二％である。そして実施例１と同じ条件で実施
した結果、得られた炭素繊維は、平均径が１μｍ１平均
長さが３０００μｍであり、透過電子顕Ｗｔｖ１．によ
る観察の結果、表面が粗く、毛羽立つ様相を呈していた
。収率はベンゼンに対して６５％であった。Example 4 The same equipment as in Example 1 was used, but the cylinder 12 was
- Filled with an atmosphere gas mainly composed of carbon oxide gas. This atmospheric gas composition uses a mixed gas of 97% by volume of converter gas and 3% by volume of coke oven gas, and its composition is 68% by volume of -carbon oxide gas, 13% by volume of carbon dioxide gas, and 4% by volume of hydrogen gas. 0% by volume, methane gas 1.0% by volume, and nitrogen gas 14% by volume. As a result of carrying out the experiment under the same conditions as in Example 1, the obtained carbon fibers had an average diameter of 1 μm and an average length of 3000 μm, and a transmission electron microscope Wtv1. As a result of observation, the surface appeared to be rough and fluffy. The yield was 65% based on benzene.
比較例１
実施例１と同様の装置を使用したが、ボンベコ２には、
−酸化炭素ガスを主体とした雰囲気ガスを充填した。こ
の雰囲気ガス組成は、−酸化炭素ガス２１容量％、二酸
化炭素ガス２０容量％、水素ガス４．０容量％、窒素ガ
ス５５容量％である。そして実施例１と同じ条件で実施
した結果、得られた炭素繊維は、平均径が１μｍ１平均
長さが１５００μｍであり、透過電子顕微鏡による観察
の結果、表面が平滑であった。収率はベンゼンに対して
２３％であった。Comparative Example 1 The same equipment as in Example 1 was used, but for Bombeco 2,
- Filled with an atmosphere gas mainly composed of carbon oxide gas. The atmospheric gas composition is -carbon oxide gas 21% by volume, carbon dioxide gas 20% by volume, hydrogen gas 4.0% by volume, and nitrogen gas 55% by volume. As a result of carrying out the experiment under the same conditions as in Example 1, the obtained carbon fibers had an average diameter of 1 μm and an average length of 1500 μm, and as a result of observation using a transmission electron microscope, the surface was smooth. The yield was 23% based on benzene.
比較例２
フェロセンの分解触媒を添加しないこと以外、実施例１
と同様の条件で実施した結果、得られた炭素繊維の収率
は、４０％であり、平均径が１μｍ１平均長さが２５０
μｍと収率、成長速度ともに低い値を示した。Comparative Example 2 Example 1 except that no ferrocene decomposition catalyst was added.
The yield of carbon fibers obtained was 40%, with an average diameter of 1 μm and an average length of 250 μm.
Both the yield and growth rate were low.
比較例３
実施例１と同じ装置を用い、ボンベ１２は、雰囲気ガス
として高純度水素ガスを充填しているものを使用した。Comparative Example 3 The same apparatus as in Example 1 was used, and the cylinder 12 was filled with high-purity hydrogen gas as an atmospheric gas.
フェロセンの分解触媒を添加することなく、他は実施例
１と同じ条件で実施した結果、得られた炭素繊維は平均
径が０．５μｍ、毛均長さが５００μｍであり、透過電
子顕微鏡による観察の結果、表面が平滑であった。収率
は、ベンゼンに対し４０％であった。As a result of carrying out the experiment under the same conditions as in Example 1 without adding a ferrocene decomposition catalyst, the obtained carbon fibers had an average diameter of 0.5 μm and an average hair length of 500 μm, which were observed using a transmission electron microscope. As a result, the surface was smooth. The yield was 40% based on benzene.
なお、この比較例２において、フェロセンの分解触媒と
してコバルト（ＩＩ）アセチルアセトナート塩を０．
１ｆｆｉｆｆ１％添加した場合、得られた炭素繊維は、
平均径が０．５μｍ、平均長さが２０００μｍであり、
収率はベンゼンに対して６０％であった。しかし、得ら
れた炭素繊維の表面は、平滑であった。In Comparative Example 2, cobalt (II) acetylacetonate salt was used as a ferrocene decomposition catalyst at a concentration of 0.
When 1% of 1ffiff is added, the obtained carbon fiber is
The average diameter is 0.5 μm, the average length is 2000 μm,
The yield was 60% based on benzene. However, the surface of the obtained carbon fiber was smooth.
実施例５
第２図は、本発明を実施するための装置の概略構成を示
す説明図である。図中参照符号３１は、転炉ガスホルダ
ーである。ガスホルダー３１から出た転炉ガス３２は、
除湿装置３３により脱水され、熱交換器３４を通りバー
ナー３５を介して熱風炉３６に入るようになっている。Embodiment 5 FIG. 2 is an explanatory diagram showing a schematic configuration of an apparatus for implementing the present invention. Reference numeral 31 in the figure is a converter gas holder. The converter gas 32 coming out of the gas holder 31 is
It is dehydrated by a dehumidifying device 33, passes through a heat exchanger 34, and enters a hot air stove 36 via a burner 35.
バーナー３５には、燃焼用空気が装入され、転炉ガスが
燃焼され熱風炉が加熱された後、再び転炉ガスを炉内に
導入し、炉内部を転炉ガスで置換した後、６００〜１３
００℃に昇温する。昇温された転炉ガスは、コークス炉
ガス３８及び粗ベンゼン３９とともに反応器３７に導入
される。この粗ベンゼンは、フェロセン０．４重量％、
コバルトアセチルアセトナート塩０．１重量％、チオフ
ェン０．２重量％溶解している。そしてこの反応器内で
炭素繊維の製造がなされる。反応器３７の出口と熱交換
器３４は接続され、フィルター４０に通じている。Combustion air is charged into the burner 35, the converter gas is combusted and the hot stove is heated, and then the converter gas is introduced into the furnace again to replace the inside of the furnace with the converter gas. ~13
Raise the temperature to 00℃. The heated converter gas is introduced into the reactor 37 together with coke oven gas 38 and crude benzene 39 . This crude benzene contains 0.4% by weight of ferrocene,
0.1% by weight of cobalt acetylacetonate salt and 0.2% by weight of thiophene are dissolved. Carbon fibers are manufactured within this reactor. The outlet of the reactor 37 and the heat exchanger 34 are connected and communicated with a filter 40 .
フィルターでは、生成した炭素繊維４３が排ガス４２と
分離される。In the filter, the generated carbon fibers 43 are separated from the exhaust gas 42.
転炉ガス３２及び空気４１を、窒素で置換された熱風炉
に２．５Ｎｍ３／ｈｒ、３．８Ｎｍ３／ｈ「の流量で導
入し、バーナーに添加した。この時炉内の温度は、１４
００℃であった。その後、転炉ガスを０１５Ｎｍ３／ｈ
ｒの流量で炉内に導入し、燃焼排ガスを置換した。次に
未加熱転炉ガスと混合し、１１５０℃に加熱された転炉
ガスを１ ＯＮｍ３／ｈ ｒの流量で反応器に導入した
。熱風炉内温度が１２００℃に達したら、再び同じ条件
で熱風炉の燃焼、転炉ガス置換、送風のサイクルを２塔
の熱風炉で交互に繰返し、反応器に導入される転炉ガス
温度を１１５０℃に保持した。反応器が予熱された後、
コークス炉ガスを０． ５Ｎｍ３／ｈｒの流量で炉内に
吹き込んだ。その後フェロセン０．４重量％、コバルト
アセチルアセトナート塩０．１゛重量％、チオフェン０
．２重量％溶解した粗ベンゼンを３．３ｋｇ／ｈｒの流
量で吹き込んだ。フィルター４０の下部より得られた微
細な綿状物を抜き出したところ、糸径１μｍ、繊維長さ
１０００μｍ以上の炭素繊維であった。Converter gas 32 and air 41 were introduced into a hot blast furnace purged with nitrogen at flow rates of 2.5 Nm3/hr and 3.8 Nm3/h, and added to the burner. At this time, the temperature inside the furnace was 14
It was 00℃. After that, converter gas is 015Nm3/h
It was introduced into the furnace at a flow rate of r to replace the combustion exhaust gas. Next, converter gas mixed with unheated converter gas and heated to 1150° C. was introduced into the reactor at a flow rate of 1 ONm 3 /hr. When the temperature inside the hot blast furnace reaches 1200℃, the cycle of combustion in the hot blast furnace, converter gas replacement, and air blowing is repeated alternately in the two hot blast furnaces under the same conditions, and the temperature of the converter gas introduced into the reactor is increased. The temperature was maintained at 1150°C. After the reactor is preheated,
Coke oven gas 0. It was blown into the furnace at a flow rate of 5 Nm3/hr. Then 0.4% by weight of ferrocene, 0.1% by weight of cobalt acetylacetonate salt, 0% by weight of thiophene.
．． Crude benzene dissolved at 2% by weight was blown in at a flow rate of 3.3 kg/hr. When the fine flocculent material obtained from the lower part of the filter 40 was extracted, it was found to be carbon fiber with a thread diameter of 1 μm and a fiber length of 1000 μm or more.
−時間の運転により、１．３２ｋｇの炭素繊維が得られ
た。また透過電子顕微鏡による観察の結果、表面が粗く
毛羽立つ様相を呈していた。- hours of operation yielded 1.32 kg of carbon fiber. Further, as a result of observation using a transmission electron microscope, the surface appeared to be rough and fluffy.
第１図は、本発明方法を実施するための装置の概略を示
す説明図、第２図は本発明方法を実施するため・の別の
装置の°概略を示す説明図である。
１１・・・アルゴンガスボンベ、１２・・・キャリヤー
ガスボンベ、１３．１４・・・流量計、１５・・・原料
タンク、１６．１７・・・ステンレス製パイプ、２０・
・・反応管、２１・・・捕集器、２２・・・ケミカルポ
ンプ、２３・・・電気炉、２４・・・熱電対、２５・・
・温度制御器、３１・・・ガスホルダー ３２・・・転
炉ガス、３３・・・脱湿装置、３４・・・熱交換器、３
５・・・バーナー ３６・・・熱風炉、３７・・・反応
器、３８・・・コークス炉ガス、３９・・・原料油、４
０・・・フィルター、４１・・・燃焼用空気、４２・・
・燃焼排ガス、４３・・・気相成長炭素繊維
出願人代理人 弁理士 鈴江武彦FIG. 1 is an explanatory diagram schematically showing an apparatus for implementing the method of the present invention, and FIG. 2 is an explanatory diagram schematically showing another apparatus for implementing the method of the present invention. 11... Argon gas cylinder, 12... Carrier gas cylinder, 13.14... Flow meter, 15... Raw material tank, 16.17... Stainless steel pipe, 20...
...Reaction tube, 21...Collector, 22...Chemical pump, 23...Electric furnace, 24...Thermocouple, 25...
・Temperature controller, 31... Gas holder 32... Converter gas, 33... Dehumidifier, 34... Heat exchanger, 3
5... Burner 36... Hot stove, 37... Reactor, 38... Coke oven gas, 39... Raw material oil, 4
0... Filter, 41... Combustion air, 42...
・Combustion exhaust gas, 43...Patent attorney Takehiko Suzue, attorney for the vapor grown carbon fiber applicant
Claims (9)
し、炭化水素の熱分解で得られた炭素を、有機金属化合
物の熱分解で生成された浮遊微粒子上に成長させて炭素
繊維を製造する方法において、 前記反応容器内に、前記有機金属化合物の分解触媒であ
る金属化合物を添加することを特徴とする炭素繊維の製
造方法。(1) Carbon fibers are produced by introducing hydrocarbons and organometallic compounds into a reaction vessel, and growing carbon obtained by thermal decomposition of the hydrocarbons on floating particles generated by thermal decomposition of the organometallic compounds. A method for producing carbon fibers, characterized in that a metal compound that is a decomposition catalyst for the organometallic compound is added into the reaction vessel.
０．０１〜５０モル添加する特許請求の範囲第１項記載
の炭素繊維の製造方法。(2) The method for producing carbon fibers according to claim 1, wherein 0.01 to 50 moles of a metal compound is added to 1 mole of the organometallic compound.
容積％で一酸化炭素５０〜８０％と二酸化炭素５〜３０
％とを少なくとも含む組成として、上記雰囲気ガスによ
り炭素繊維の表面修飾をおこなうことを特徴とする特許
請求の範囲第１項記載の炭素繊維の製造方法。(3) The composition of the atmospheric gas introduced into the reaction vessel is
Carbon monoxide 50-80% and carbon dioxide 5-30% by volume
%. The method for producing carbon fibers according to claim 1, wherein the surface of the carbon fibers is modified by the atmospheric gas.
に対して、二酸化炭素０．０６〜０．６部、水素０．０
０１〜０．２部を少なくとも含む組成として、上記雰囲
気ガスにより炭素繊維の表面修飾をおこなうことを特徴
とする特許請求の範囲第１項記載の炭素繊維の製造方法
。(4) The composition of the atmospheric gas is 1 part of carbon monoxide, 0.06 to 0.6 part of carbon dioxide, and 0.0 part of hydrogen.
2. The method for producing carbon fibers according to claim 1, wherein the carbon fibers are surface-modified using the atmospheric gas as a composition containing at least 0.01 to 0.2 parts.
物ガス、及びこれらのガスに水素含有ガスを混合したガ
スの群から選択された単独あるいは混合ガスのうち１つ
のガスである特許請求の範囲第３項又は第４項記載の炭
素繊維の製造方法。(5) A patent claim in which the atmospheric gas is one gas selected from the group consisting of converter gas, a mixture gas with blast furnace gas, and a mixture of these gases and a hydrogen-containing gas, either singly or in a mixture. The method for producing carbon fiber according to item 3 or 4.
範囲第５項記載の炭素繊維の製造方法。(6) The method for producing carbon fiber according to claim 5, wherein the hydrogen-containing gas is coke oven gas.
を熱風炉で加熱した後に反応容器内に導入する特許請求
の範囲第３項また又は第４項記載の炭素繊維の製造方法
。(7) The method for producing carbon fibers according to claim 3 or 4, wherein the atmospheric gas is stored in a gas tank, heated in a hot air oven, and then introduced into the reaction vessel.
雰囲気ガスを交互に導入して加熱した後に反応容器内に
導入する特許請求の範囲第７項記載の炭素繊維の製造方
法。(8) The method for producing carbon fibers according to claim 7, wherein at least two hot blast stoves are provided, and atmospheric gas is alternately introduced into each hot blast stove for heating and then introduced into a reaction vessel.
℃でおこなう特許請求の範囲第１項記載の炭素繊維の製
造方法。(9) Thermal decomposition of the aromatic hydrocarbon is performed at a temperature of 600 to 1300
A method for producing carbon fiber according to claim 1, which is carried out at a temperature of .degree.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63228061A JPH0680210B2 (en) | 1988-09-12 | 1988-09-12 | Carbon fiber manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63228061A JPH0680210B2 (en) | 1988-09-12 | 1988-09-12 | Carbon fiber manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0280619A true JPH0280619A (en) | 1990-03-20 |
| JPH0680210B2 JPH0680210B2 (en) | 1994-10-12 |
Family
ID=16870582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63228061A Expired - Lifetime JPH0680210B2 (en) | 1988-09-12 | 1988-09-12 | Carbon fiber manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0680210B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061706C (en) * | 1996-06-19 | 2001-02-07 | 中国科学院金属研究所 | Preparation process of gas-phase grown nanometer carbon fibre |
| CN101941695A (en) * | 2010-09-09 | 2011-01-12 | 北京化工大学 | Method for synthesizing graphene |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60181319A (en) * | 1984-02-21 | 1985-09-17 | Nikkiso Co Ltd | Manufacture of carbon fiber by vapor-phase process |
| JPS61225320A (en) * | 1985-03-23 | 1986-10-07 | Asahi Chem Ind Co Ltd | Metal-containing carbonaceous fiber and production thereof |
| JPS62238826A (en) * | 1986-04-01 | 1987-10-19 | Asahi Chem Ind Co Ltd | Production of carbon fiber |
| JPS62250225A (en) * | 1986-04-22 | 1987-10-31 | Nippon Kasei Kk | Production method for carbon fiber by vapor-phase pyrolysis |
| JPS6312720A (en) * | 1986-06-27 | 1988-01-20 | Nippon Kokan Kk <Nkk> | Production of carbon fiber grown in gaseous phase |
-
1988
- 1988-09-12 JP JP63228061A patent/JPH0680210B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60181319A (en) * | 1984-02-21 | 1985-09-17 | Nikkiso Co Ltd | Manufacture of carbon fiber by vapor-phase process |
| JPS61225320A (en) * | 1985-03-23 | 1986-10-07 | Asahi Chem Ind Co Ltd | Metal-containing carbonaceous fiber and production thereof |
| JPS62238826A (en) * | 1986-04-01 | 1987-10-19 | Asahi Chem Ind Co Ltd | Production of carbon fiber |
| JPS62250225A (en) * | 1986-04-22 | 1987-10-31 | Nippon Kasei Kk | Production method for carbon fiber by vapor-phase pyrolysis |
| JPS6312720A (en) * | 1986-06-27 | 1988-01-20 | Nippon Kokan Kk <Nkk> | Production of carbon fiber grown in gaseous phase |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061706C (en) * | 1996-06-19 | 2001-02-07 | 中国科学院金属研究所 | Preparation process of gas-phase grown nanometer carbon fibre |
| CN101941695A (en) * | 2010-09-09 | 2011-01-12 | 北京化工大学 | Method for synthesizing graphene |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0680210B2 (en) | 1994-10-12 |
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