JPS6392726A - Production of carbon fiber by vapor process - Google Patents
Production of carbon fiber by vapor processInfo
- Publication number
- JPS6392726A JPS6392726A JP23375886A JP23375886A JPS6392726A JP S6392726 A JPS6392726 A JP S6392726A JP 23375886 A JP23375886 A JP 23375886A JP 23375886 A JP23375886 A JP 23375886A JP S6392726 A JPS6392726 A JP S6392726A
- Authority
- JP
- Japan
- Prior art keywords
- transition metal
- droplet
- carbon fiber
- metal compound
- seeds
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 13
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 title abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 21
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 20
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 12
- 150000003624 transition metals Chemical class 0.000 claims abstract description 9
- 239000002134 carbon nanofiber Substances 0.000 claims description 25
- 238000000197 pyrolysis Methods 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 11
- 239000002923 metal particle Substances 0.000 claims description 5
- 239000011882 ultra-fine particle Substances 0.000 claims description 4
- 239000012808 vapor phase Substances 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000001947 vapour-phase growth Methods 0.000 abstract 2
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 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 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 239000012159 carrier gas Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000009834 vaporization Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 etc. are used Chemical class 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 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
- D01F9/1276—Aromatics, e.g. toluene
-
- 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】
〔産業上の利用分野〕
本発明は気相法炭素繊維、特に極微細な気相洗炭Ｍ＃Ｉ
雑を効率よくつくることが出来る改良された方法に関す
る。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to vapor-grown carbon fibers, particularly ultrafine vapor-washed carbon M#I.
This invention relates to an improved method for efficiently producing miscellaneous materials.
従来、気相法炭素ｉｌ帷を製造する場合には、遷移金属
元素の超微粒子をシードとして用い、これに炭素を析出
、生長させて炭素繊維とするが、その製造法としては、
■熱分解炉中の基板上に「ｅ等の遷移金属元素の超微粉
末を散布してシードとして用いる方法（特開昭５２−１
０３５２８ ＠−全公報、■ｌ”ｅ等の遷移金属化合物
を気化させ、キ１！リヤガスとともに熱分解炉内に送入
しシードを生成させて用いる方法（特開昭６０−５４９
９８号公報）、■Ｆｅ等の遷移金属化合物を液体有機化
合物の分散或は溶解させて熱分解炉中にスプレーしてシ
ードを生成させて用いる方法（特開昭５８−１８０６１
５＠公報）などがある。Conventionally, when manufacturing vapor-grown carbon il cloth, ultrafine particles of transition metal elements are used as seeds, and carbon is precipitated and grown to form carbon fibers, but the manufacturing method is as follows:
■A method of scattering ultrafine powder of transition metal elements such as e on a substrate in a pyrolysis furnace and using it as a seed (Japanese Patent Laid-Open No. 52-1
03528 @-Zen Publication, ■Method of vaporizing transition metal compounds such as l”e and feeding them into a pyrolysis furnace together with Kiriya gas to generate seeds (Japanese Unexamined Patent Publication No. 60-549)
98 Publication), ■ A method of using a transition metal compound such as Fe by dispersing or dissolving it in a liquid organic compound and spraying it into a pyrolysis furnace to generate seeds (Japanese Patent Laid-Open No. 58-18061
5@public bulletin).
これらの方法らおいては、いずれも１１００〜１３００
℃の反応空間に活性なＦｅシードと炭素源となる有機化
合物とを共存させることが必須である。In these methods, 1100 to 1300
It is essential that an active Fe seed and an organic compound serving as a carbon source coexist in the reaction space at .degree.
■の基板にシードを散布する方法は、［ｅの超微粉末を
用いることが重要で、細い程炭素繊維の生成効率がよい
。しかし、最も細かいＦｅ粉末は相対比で、粒径１００
人： ２００人＝３００人＝１０＝２〜７：１〜６で、
これより細いものは存在しないと云われている（表面Ｖ
ＯＪ２４．Ｎα５゜Ｐ２２７〜２３３）。この方法で得
られる炭素繊維は、直径１０〜３０μｍ、長さ１０〜２
０１で、肉眼で炭素繊維とわかるものが得られる。■の
気化法、■のスプレー法で得られる炭素繊維は、−見煤
状であるが、ＳＥＭなどで拡大して見ると繊維であるこ
とが確認でき、径が０．１〜０．２μｍ１長さが数Ｍで
湾曲、分岐を有しているものが多く、■の基板法でつく
られた炭素ｌｌＮに比して、はるかに微細であるが、収
率、生産性が高いのが特徴である。In the method (2) of dispersing seeds on a substrate, it is important to use ultrafine powder (e), and the finer the powder, the better the carbon fiber production efficiency. However, in relative terms, the finest Fe powder has a particle size of 100
People: 200 people = 300 people = 10 = 2-7: 1-6,
It is said that there is nothing thinner than this (surface V
OJ24. Nα5°P227-233). The carbon fiber obtained by this method has a diameter of 10 to 30 μm and a length of 10 to 2
01, a material that can be recognized with the naked eye as carbon fiber is obtained. The carbon fibers obtained by the vaporization method in ① and the spray method in ② have a soot-like appearance, but when viewed under magnification using an SEM, they can be confirmed to be fibers, with a diameter of 0.1 to 0.2 μm and a length. Many of them have a length of several M and are curved and branched, and are much finer than the carbon 1N produced by the substrate method in (2), but are characterized by high yield and productivity. be.
上記気相法炭素繊維は、周知のようにシードを炭素！！
雑の先端につけて生長するが、繊維先端部に残っている
Ｆｅシードの大きさを透過電子顕微鏡で観察すると、そ
の径は５０〜１５０人である。As is well known, the vapor-grown carbon fiber mentioned above uses carbon as a seed! !
The size of the Fe seeds remaining at the tips of the fibers is observed using a transmission electron microscope, and the diameter is 50 to 150.
したがって、効率よく気相法炭素［１を得るには、５０
〜１５０Ａ径のｌ”ｅシードを収率よく得ることが必要
である。したがって、粒度分布を２０〜３００人と調整
すると、５０〜１５０人の粒子の割合が多くなるので好
ましい。Therefore, in order to efficiently obtain vapor-grown carbon [1], 50
It is necessary to obtain l''e seeds with a diameter of ~150A in good yield. Therefore, it is preferable to adjust the particle size distribution to 20-300 particles, since this increases the proportion of particles with 50-150 particles.
上記３つの方法におけるＦｅシードの利用効率を求める
と、■の基板を用いる方法は３．３×１０ 、■の気
化法は３．７Ｘ １０−’ 、■のスプレー法は２．６
Ｘ１０’となった。The utilization efficiency of Fe seeds in the above three methods is 3.3 x 10 for the method using a substrate, 3.7 x 10 -' for the vaporization method, and 2.6 for the spray method.
It became X10'.
但し、上記利用効率は、次のようにして求めたものであ
る。すなわち、
■の基板法では、０．１％のｌ”ｅ超微粒子を含むエタ
ノールを基板上にスプレーしてシードとし、生成炭素繊
維と推定シードの数との比より求めた。However, the above usage efficiency was determined as follows. That is, in the substrate method (2), ethanol containing 0.1% l''e ultrafine particles was sprayed onto the substrate to serve as seeds, and the number was determined from the ratio of the produced carbon fibers to the estimated number of seeds.
■の気化法では気化させることにより、分圧でベンゼン
９５ ｔｏｒｒ１フェロセン５９ ｔｏｒｒを含むＨ２
ガスをつくり、これを熱分解炉に送り、生成炭素繊維の
本数と、フェロセンの供給最のバランスから、すべての
Ｆｅが径１００人のＦｅシードとなったと仮定して、そ
の数との比より算出した。In the vaporization method (2), by vaporizing H2 containing benzene 95 torr1 ferrocene 59 torr at a partial pressure
Create a gas, send it to the pyrolysis furnace, and from the balance between the number of carbon fibers produced and the best supply of ferrocene, assuming that all Fe becomes Fe seeds with a diameter of 100 people, the ratio to that number is Calculated.
■のスプレー法では、０．２ｗｔ％のフェロセンを含む
ベンゼン溶液を熱分解炉内にスプレーして反応させ、生
成炭素ａｍの本数と、フェロセンのＦｅが仝け１００人
のＦｅシードとなったと仮定して、その数との比より算
出した。In the spray method (2), a benzene solution containing 0.2 wt% ferrocene is sprayed into the pyrolysis furnace to cause a reaction, and it is assumed that the number of produced carbon am and the Fe of ferrocene become 100 Fe seeds. It was calculated from the ratio to that number.
以上の結果より■のスプレー法のシード利用効率が格段
に高いことがわかる。From the above results, it can be seen that the seed usage efficiency of the spray method (■) is significantly high.
■の基板法において、使用されるＦｅシードの平均粒径
は１５０人であるが、スート状のもので、実際に利用さ
れる部分は少なく、また、■の気化法は、Ｆｅシードが
生成するのに時間を要し、相当部分がシードとなる前に
反応域を通過するため、利用効率が低いものと思われる
。未利用のｌ”ｅは、製品の炭素繊維に付着回収されて
、不純物増加の原因にもなって、好ましい形ではない。In the substrate method (2), the average particle size of the Fe seeds used is 150 particles, but they are in the form of soot, and the portion that is actually used is small, and in the vaporization method (2), the Fe seeds are The utilization efficiency is thought to be low because it takes time to process and a considerable portion passes through the reaction zone before becoming seeds. Unused l''e is collected and attached to the carbon fibers of the product, causing an increase in impurities, which is not a desirable form.
上記気相法炭素繊維の！ｌｌ造に用いられるＦｅシード
は、いずれもコストが高く、気相法炭素繊維のコストに
占める割合は比較的大きく、シードを有効利用すること
は重要である。The above vapor grown carbon fiber! The cost of Fe seeds used in Il manufacturing is high, and their proportion in the cost of vapor-grown carbon fiber is relatively large, so it is important to use the seeds effectively.
本発明は上記の事情に鑑み、スプレー法のシード利用効
率が高いことに着目し、これを改良してさらにこれを高
め、操作の容易な気相法炭素繊維の製造法を提供するこ
とを目的とする。In view of the above-mentioned circumstances, the present invention focuses on the high seed utilization efficiency of the spray method, and aims to improve this to further increase this and provide an easy-to-operate method for producing vapor-grown carbon fiber. shall be.
（問題点を解決するための手段〕
本発明はシードとして、径５０〜１５０人のものが特に
有効であることから、スプレー法によってこれをつくる
ことを考え、到達したものである。(Means for Solving the Problems) The present invention was developed based on the idea that seeds with a diameter of 50 to 150 are particularly effective, and that they can be produced by a spray method.
本発明者等の研究により、液滴が蒸発した際、多くは１
個の液滴中に含まれる金属が凝集（融合等を含む）して
粒子をつくり、かつ一つの液滴が他の液滴からの金属と
凝集することは少ないことが判明した。したがって、金
属粒子の大きさは、液滴の大・きざと、その中の濃度と
の函数であり、その大きさを調整することが出来る。According to the research conducted by the present inventors, when a droplet evaporates, in most cases 1
It has been found that metals contained in individual droplets aggregate (including fusion, etc.) to form particles, and that one droplet rarely aggregates with metals from other droplets. Therefore, the size of the metal particles is a function of the size and size of the droplet and the concentration therein, and the size can be adjusted.
すなわち、本発明の要旨は、遷移金属の化合物を含有す
る液体有機化合物の微小液滴を熱分解炉内に分散し、遷
移金属元素の超微粒子をシードとして有機化合物の気相
熱分解により炭素繊維を製造する方法において、上記液
滴の大きざ及び遷移金属化合物の温度を液滴中に含まれ
ている遷移金属の原子が熱分解炉内で凝集して、該金属
粒子を形成したとき、その粒子の大きざの分布が２０Å
〜３００人となるように調整する気相法炭素繊維の製造
法にある。That is, the gist of the present invention is to disperse micro droplets of a liquid organic compound containing a compound of a transition metal in a pyrolysis furnace, and to produce carbon fibers by vapor phase pyrolysis of the organic compound using ultrafine particles of a transition metal element as seeds. In the method for producing a metal particle, the size of the droplet and the temperature of the transition metal compound are determined by adjusting the size of the droplet and the temperature of the transition metal compound when the atoms of the transition metal contained in the droplet aggregate in a pyrolysis furnace to form the metal particles. Particle size distribution is 20 Å
The method for producing vapor-grown carbon fiber is to adjust the production time to 300 people.
以下本発明を具体的に説明する。 The present invention will be specifically explained below.
本発明に用いられる遷移金属化合物は、Ｆｅ２Ｏ３等液
体有機化合物に不溶なものも、キャリヤガスとしてＨ２
を用いれば還元されてＦｅとなるので使用可能であるが
、均一分散を考慮すると、液体有機化合物に溶解する遷
移金属化合物が望ましい。The transition metal compounds used in the present invention may be insoluble in liquid organic compounds such as Fe2O3 or H2 as a carrier gas.
However, in consideration of uniform dispersion, it is desirable to use a transition metal compound that dissolves in a liquid organic compound.
液体有機化合物としては、炭化水素、０．Ｎ。Liquid organic compounds include hydrocarbons, 0. N.
Ｓ等を有する有様化合物、或はアルコール類等が用いら
れるが、特にベンゼン等の炭化水素が、炭素の割合が多
（好ましい。Compounds having S or the like, alcohols, etc. are used, and hydrocarbons such as benzene are particularly preferred since they have a large proportion of carbon.
また、キャリヤガスとしては、従来、気相法炭素繊維（
以下ＶＧＣＦという）の製法において使用されるものが
いずれも使用出来、通常Ｈ２が用いられる。In addition, conventionally, vapor grown carbon fiber (
Any of those used in the manufacturing method of VGCF (hereinafter referred to as VGCF) can be used, and H2 is usually used.
次にＶＧＣＦの製造に用いる装置を説明する。Next, the apparatus used for manufacturing VGCF will be explained.
第１図は外熱型反応装置の一例を示すもので、図中符号
１はムライト等によってつくられた熱分解炉である。熱
分解炉１の外周には、内部を１１００〜１３００℃に加
熱するヒータ２が取付けられている。また上記熱分解炉
１の一端には噴霧器３が取付けられ、他端にはガスの排
出管４が取付けられている。FIG. 1 shows an example of an external thermal reactor, and the reference numeral 1 in the figure is a thermal decomposition furnace made of mullite or the like. A heater 2 is attached to the outer periphery of the pyrolysis furnace 1 to heat the inside to 1100 to 1300°C. Further, a sprayer 3 is attached to one end of the pyrolysis furnace 1, and a gas discharge pipe 4 is attached to the other end.
上記噴霧器３にはキャリヤガス５および容器６に貯留さ
れた遷移金属化合物を所定の濃度に溶解した液体有機化
合物６ａが導入され、熱分解炉１内に噴霧される。A carrier gas 5 and a liquid organic compound 6a in which a transition metal compound stored in a container 6 is dissolved to a predetermined concentration are introduced into the sprayer 3 and sprayed into the pyrolysis furnace 1.
上記噴霧器３は、後述する理由により、噴霧によって生
ずる液滴を計５〜３０μｍとしなければならないが、通
常の噴霧器では生成する液滴が数１００μｍとなり、■
ｄＣＦの生成効率が低下する。そのため２液、或は多液
混合型アトマイザ−を用いるのが好ましい。この混合型
のアトマイザ−は、径５〜２０００μｍの間の任意の狭
い範囲の液滴が容易に４りられるので本発明の方法に好
適に利用出来る。さらに分散をよくするため超音波発信
器を用いるか、或は超音波発信器ど他の分散装置とを併
用してもよい。The above-mentioned sprayer 3 must generate droplets with a total size of 5 to 30 μm for the reasons described below, but with a normal sprayer, the droplets generated are several 100 μm, and
The production efficiency of dCF decreases. Therefore, it is preferable to use a two-liquid or multi-liquid mixing type atomizer. This mixed type atomizer can be suitably used in the method of the present invention because it can easily form droplets in any narrow range between 5 and 2000 μm in diameter. Furthermore, in order to improve the dispersion, an ultrasonic transmitter may be used, or another dispersion device such as an ultrasonic transmitter may be used in combination.
また、上記液体有機化合物中の遷移金属化合物の濃度は
、シードの利用効率を高めるため、各液滴中の遷移金属
化合物が熱分解して、５０〜１５０Ａの金属シードとな
ることが必要であり、液滴の径が小さい程その濃度は高
くなる。したがって、液滴が５〜３０μｍの場合、これ
に含まれる繊維化合物は、５０〜１００人の金属シード
を生成する濃度が望ましい。しかし、遷移金属化合物中
の金属がすべて遷移金属粒子となるのではなく、一部は
蒸発してしまうのでイの分を見込むと、０．０１〜１．
０ＩＩＯＪ／Ｊの範囲が適当である。In addition, the concentration of the transition metal compound in the liquid organic compound must be such that the transition metal compound in each droplet is thermally decomposed to become a metal seed of 50 to 150 A in order to increase the efficiency of seed utilization. , the smaller the diameter of the droplet, the higher its concentration. Therefore, when the droplet is 5 to 30 μm, the fiber compound contained therein is preferably at a concentration that produces 50 to 100 metal seeds. However, not all of the metal in the transition metal compound becomes transition metal particles, but some of it evaporates, so if we take into account the amount of (a), it is 0.01 to 1.
A range of 0IIOJ/J is appropriate.
上記液滴の径が５μｍ未満では、シードに対するＣ源の
聞が不足し、３０μｍを越えると液体有機化合物の蒸発
に時間がかかるばかりでなく、落下速度が早くなり、共
にＶＧＣＦの生成効率、シードの利用率が低下する。If the diameter of the droplet is less than 5 μm, there will be insufficient space between the C source and the seed, and if it exceeds 30 μm, not only will it take time to evaporate the liquid organic compound, but the droplet speed will increase, which will reduce the production efficiency of VGCF and the seed. utilization rate will decrease.
上記装置を用いてＶＧＣＦを製造するには、先ず熱分解
炉１を１１００〜１３００℃に加熱し、所定量のキャリ
ヤガスとともに所定量の右撮化合物溶液６ａを噴霧する
。噴霧によって生成した液ｗ！４７は加熱され、沸点の
低い有機化合物の蒸発が進行する。さらに蒸発が進むと
遷移金属化合物の蒸発がはじまるが、高温雰囲気内の微
粒子であり、温度上昇が急激であるため、他の方法に比
べて格段に簡単、かつ再現性よく遷移金属原子集団の微
粒子が生成される。この生成された金属原子微粒子は、
液滴中の遷移金属化合物濃度が調整されているので、５
０〜１００人の範囲のシードが効率よく得られ、かつこ
のシードはＣ瞭となる有機化合物蒸気中にある。したが
って、シードの利用率が高く、ＶＧＣＦ８が効率よく生
成される。To produce VGCF using the above-mentioned apparatus, first, the pyrolysis furnace 1 is heated to 1100 to 1300° C., and a predetermined amount of the compound solution 6a is sprayed together with a predetermined amount of carrier gas. Liquid generated by spraying lol! 47 is heated, and evaporation of organic compounds with low boiling points progresses. As the evaporation progresses further, the transition metal compound begins to evaporate, but since the particles are in a high-temperature atmosphere and the temperature rises rapidly, it is much simpler and more reproducible than other methods to produce fine particles of transition metal atomic groups. is generated. This generated metal atomic fine particle is
Since the concentration of transition metal compound in the droplet is adjusted, 5
Seeds ranging from 0 to 100 are efficiently obtained, and the seeds are in a vapor of organic compounds that are carbonaceous. Therefore, the seed utilization rate is high and VGCF8 is efficiently generated.
上記方法は、Ｆｅ、Ｎｉ 、Ｇｏ、Ｖ、 Ｔａ。The above method applies to Fe, Ni, Go, V, Ta.
Ｍｏ、Ｃｒ等の遷移金属超微粉末を上記液体有機化合物
に懸濁し、これを噴霧しても比較的効率よ＜ＶＧＣＦが
得られるが、これら金属のシードに適した微粉末は高価
で、ＶＧＣＦのコスト上昇につながり好ましくない。Even if ultrafine powder of transition metals such as Mo and Cr are suspended in the liquid organic compound and sprayed, VGCF can be obtained relatively efficiently, but fine powders suitable for seeds of these metals are expensive, and VGCF is This is undesirable as it leads to an increase in costs.
第２図は、内熱型反応装置を示すもので、第１図のヒー
タ２の代りに、酸水素バーナ９を設けたもので、第１図
と同一部分には同一符号を付してその説明を省略する。Fig. 2 shows an internal heating type reactor, in which an oxyhydrogen burner 9 is provided in place of the heater 2 in Fig. 1, and the same parts as in Fig. 1 are denoted by the same reference numerals. The explanation will be omitted.
次に実施例を示して本発明を説明する。 Next, the present invention will be explained with reference to Examples.
実施例１
径２００ＩＩＩＲ１長さ１５００ｍの第１図に示す装置
を用いＶＧＣＦの！Ｊ造を行なった。Example 1 Using the apparatus shown in Fig. 1 with a diameter of 200 m and a length of 1,500 m, VGCF! J construction was carried out.
噴霧器としては、原子吸光分析に使用する小型２液体式
アトマイザを用い、約１２００℃に保持された熱分解炉
１内に、フェロセン１ｗｔ％を溶解したベンゼンを３ｃ
ｃ／分で供給し、キャリヤガス５としてＨ２を５１７分
で流して反応を行なった。A small two-liquid atomizer used for atomic absorption spectrometry was used as the atomizer, and 3 c of benzene in which 1 wt% of ferrocene was dissolved was placed in the pyrolysis furnace 1 maintained at about 1200°C.
The reaction was carried out by supplying H2 as a carrier gas at 517 min.
３分間反応させた後、炉内および炉底に堆積したＶＧＣ
Ｆを回収して重量を測定した結果、６ｇであった。これ
をＳＥＭｒｌ察したところ、径０．１〜０．１５μ瓦の
からまったｍ維であり、ＦＱの利用率は、５．２Ｘ １
０−であった。VGC deposited inside the furnace and at the bottom of the furnace after reacting for 3 minutes
As a result of collecting F and measuring its weight, it was 6 g. SEMrl analysis of this revealed that it was a tangled fiber with diameters of 0.1 to 0.15μ, and the FQ utilization rate was 5.2X 1
It was 0-.
また同じ条件で常温空間に噴霧し、液層の大きさを測定
したところ１０〜２０μｍであった。Furthermore, when the liquid layer was sprayed into a room temperature space under the same conditions and the size of the liquid layer was measured, it was 10 to 20 μm.
実施例２
径５００＃Ｉ、長さ１５００顛の第２図に示す装置を用
いＶＧＣＦを製造した。Example 2 A VGCF was manufactured using the apparatus shown in FIG. 2 with a diameter of 500 #I and a length of 1500 #I.
先ず酸水素バーナ９によって炉内温度を１２００〜１３
００℃とし、この空間にフェロセンを１ｗｔ％、Ｓを０
．０５ ｗｔ％含むベンゼンを１０ＣＣ／分の速度で供
給し、キャリヤガス５としてＨ２を１５Ｊ／分で流して
反応を行なった。３分間反応させた後、炉内に生成した
ＶＧＣＦを回収し重量を測定したところ２２９であった
。これをＳＥＭで観察した結果は、実施例１と同様の繊
帷で、ｌ”ｅの利用率は５．８Ｘ １０″４であった。First, the temperature inside the furnace is set to 1200 to 13
00℃, 1wt% ferrocene and 0 S in this space.
．． Benzene containing 0.05 wt% was supplied at a rate of 10 CC/min, and H2 was flowed as a carrier gas 5 at a rate of 15 J/min to carry out the reaction. After reacting for 3 minutes, the VGCF produced in the furnace was collected and its weight was measured and found to be 229. Observation of this with a SEM revealed that the fabric was the same as in Example 1, with a utilization rate of 1"e of 5.8X 10"4.
実施例３
ベンゼンの代りに、ナフサを用いた他は実施例１と同様
にしてＶＧＣＦをつくった。得られたＶＧＣＦは５ｇ、
Ｆｅの利用率は４．３Ｘ１０’であった。Example 3 VGCF was produced in the same manner as in Example 1 except that naphtha was used instead of benzene. The obtained VGCF was 5 g,
The utilization rate of Fe was 4.3×10′.
実施例４
フェロセンの代りに、Ｃｒのメタロセンを用いた他は実
施例１と同じにしてＶＧＣＦをつくり、はぼ同様な結果
を得た。Example 4 VGCF was produced in the same manner as in Example 1 except that Cr metallocene was used instead of ferrocene, and almost the same results were obtained.
実施例５
アトマイザの代りに、超音波発行器を用いて、ベンゼン
溶液をミスト化した他は実施例１と同じにしたところ、
ＶＧＣＦ５ｇを得た。Example 5 The same procedure as Example 1 was carried out except that an ultrasonic generator was used instead of the atomizer to turn the benzene solution into a mist.
5 g of VGCF was obtained.
実施例６
アトマイザの代りに、高圧スプレー装置を用いた他は実
施例１と同一条件で行なった所、３分間でＶＧＣＦ３〜
４ｇを得た。Example 6 The same conditions as Example 1 were used except that a high-pressure spray device was used instead of the atomizer.
4g was obtained.
以上述べたように、本発明の方法はＶＧＣＦのシードと
なる遷移金属微粉末が容易かつ効率よく生成され、生成
されたシードの周囲にはＣ源となる有機化合物蒸気が存
在するので、効率よくＶＧＣＦが生成され、また遷移全
屈のシードとしての利用率も高く、ＶＧＣｒ’のコスト
を大幅に低下することが出来る。As described above, in the method of the present invention, fine transition metal powders that serve as seeds for VGCF are easily and efficiently generated, and organic compound vapor that serves as a C source exists around the generated seeds. VGCF is generated, and the utilization rate as a seed for transition total bending is high, and the cost of VGCr' can be significantly reduced.
第１図および第２図は、本発明の方法を実施する装置の
例を示す図で、第１図は外熱型装置の図、第２図は内熱
型装置の図である。
１・・・・・・熱分解炉、２・・・・・・ヒータ、３・
・・・・・噴霧器、４・・・・・・ガス排出管、５・・
・・・・キャリヤガス、６・・・・・・容器、６ａ・・
・・・・遷移金属化合物の液体有様化合物溶液、７・・
・・・・液滴、８・・・・・・気相法炭素ｔａ維（ＶＧ
ＣＦ）、９・・・・・・酸水素バーナ。FIGS. 1 and 2 are diagrams showing examples of apparatus for carrying out the method of the present invention, with FIG. 1 being an external heating type apparatus and FIG. 2 being an internal heating type apparatus. 1...Pyrolysis furnace, 2...Heater, 3.
...Sprayer, 4...Gas exhaust pipe, 5...
...Carrier gas, 6...Container, 6a...
...Liquid state compound solution of transition metal compound, 7...
...Droplet, 8...Vapour-grown carbon ta fiber (VG
CF), 9... Oxygen hydrogen burner.
Claims (2)
小液滴を熱分解炉内に分散し、遷移金属元素の超微粒子
をシードとして有機化合物の気相熱分解により炭素繊維
を製造する方法において、上記液滴の大きさ及び遷移金
属化合物の濃度を液滴中に含まれている遷移金属の原子
が熱分解炉内で凝集して、該金属粒子を形成したとき、
その粒子の大きさの分布が２０Å〜３００Åとなるよう
に調整することを特徴とする気相法炭素繊維の製造法。(1) In a method of manufacturing carbon fiber by vapor phase pyrolysis of the organic compound by dispersing micro droplets of a liquid organic compound containing a transition metal compound in a pyrolysis furnace and using ultrafine particles of a transition metal element as seeds. , the size of the droplet and the concentration of the transition metal compound when the atoms of the transition metal contained in the droplet aggregate in the pyrolysis furnace to form the metal particles,
A method for producing vapor-grown carbon fiber, which comprises adjusting the particle size distribution to be 20 Å to 300 Å.
の中の遷移金属化合物の濃度が、遷移金属原子として０
．０１ｍｏｌ／ｌ〜１．０ｍｏｌ／ｌである特許請求の
範囲第１項記載の気相法炭素繊維の製造法。(2) The diameter of the droplet is 5 μm to 30 μm, and the concentration of the transition metal compound in the liquid organic compound is 0 as transition metal atoms.
．． 01 mol/l to 1.0 mol/l, the method for producing vapor-grown carbon fiber according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23375886A JPS6392726A (en) | 1986-10-01 | 1986-10-01 | Production of carbon fiber by vapor process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23375886A JPS6392726A (en) | 1986-10-01 | 1986-10-01 | Production of carbon fiber by vapor process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6392726A true JPS6392726A (en) | 1988-04-23 |
Family
ID=16960114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23375886A Pending JPS6392726A (en) | 1986-10-01 | 1986-10-01 | Production of carbon fiber by vapor process |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6392726A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003002789A1 (en) * | 2001-06-28 | 2003-01-09 | Showa Denko K.K. | Method and apparatus for producing vapor grown carbon fiber |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57117622A (en) * | 1981-01-14 | 1982-07-22 | Showa Denko Kk | Production of carbon fiber through vapor-phase process |
-
1986
- 1986-10-01 JP JP23375886A patent/JPS6392726A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57117622A (en) * | 1981-01-14 | 1982-07-22 | Showa Denko Kk | Production of carbon fiber through vapor-phase process |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003002789A1 (en) * | 2001-06-28 | 2003-01-09 | Showa Denko K.K. | Method and apparatus for producing vapor grown carbon fiber |
| US7524479B2 (en) | 2001-06-28 | 2009-04-28 | Showa Denko K.K. | Method for producing vapor grown carbon fiber |
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