JP2019533775A - 引張強度が向上されたカーボンナノチューブ繊維の製造方法 - Google Patents
引張強度が向上されたカーボンナノチューブ繊維の製造方法 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 111
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
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- 229910052799 carbon Inorganic materials 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
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- 239000012495 reaction gas Substances 0.000 claims description 14
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
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- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/164—Preparation involving continuous processes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
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- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/06—Load-responsive characteristics
- D10B2401/063—Load-responsive characteristics high strength
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- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Carbon And Carbon Compounds (AREA)
- Inorganic Fibers (AREA)
Abstract
Description
したがって、CNT集合体繊維の引張強度を向上させるためには、反応器の内部に形成される回転流動を除去するか、抑制する必要がある。
また、前記反応管の反応領域は、1000〜3000℃または、1150〜1300℃で加熱されるものであり得る。
また、前記キャリアガスは不活性ガスをさらに含むものであり得る。
好ましくは、前記触媒または触媒前駆体がメタロセン型であり得る。
レイノルズ数:Re=wd/ν
グラスホフ数:Gr=(d3gβΔθ)/(ν2)
以下、本発明が属する技術分野で通常の知識を有する者が容易に実施できるように、本発明の実施例について詳細に説明する。しかし、本発明は様々な異なる形態で実現することができ、ここで説明する実施例に限定されない。
フェロセン触媒前駆体を0.06〜0.08g/hr、硫黄触媒活性剤を0.01〜0.03g/hrの速度で気化して投入し、炭素化合物としてメタンを1〜2hr−1のGHSVで、キャリアガス(水素)は25〜30hr−1のGHSVで、温度1170〜1250℃の垂直円筒形反応器の上部に流入させた。反応管入口と加熱炉入口との間の領域で0.007≦Gr/Re2≦0.12となるように、反応器内の温度勾配を調節して反応させた。この時、Gr=0.2〜2.1、Re=4.3〜5.4であり、反応管入口の温度を250℃とし、加熱炉入口の温度を816℃にして反応器内の温度勾配を調節した。そして、反応器の下部の排出口に排出されるカーボンナノチューブ繊維をボビン(bobbin)で構成されている巻取手段により巻いた。
加熱炉の入口領域で0.12<Gr/Re2となるように、反応器上部の温度勾配を、反応管入口の温度を250℃、加熱炉入口の温度を756℃にして調整したことを除いては、実施例1と同様に直接紡糸法によってカーボンナノチューブ繊維を合成した。
レイノルズ数:Re=wd/ν
W(炭素源を含有した反応ガス流速):温度によるガスの膨張を考慮して計算したガス流量を下記の表1に示した。
v(炭素源を含有した反応ガスの動粘性係数):温度による粘度および密度を求め、粘度と密度を分けて計算した動粘性係数を以下の表1に示した。
d(反応管内径)=0.065m
グラスホフ数:Gr=(d3gβΔθ)/(ν2)
gは重力加速度、βは炭素源を含有した反応ガスの熱膨張係数、
dは反応管内径(0.065m)、vは動粘性係数(表1参照)、
Δθ=(反応管の表面温度)−(反応器内部のガス温度)。
したがって、本発明の実質的な範囲は、添付の特許請求の範囲とそれらの等価物によって定義されると言える。
Claims (11)
- 炭素源を含む反応ガスを、触媒または触媒前駆体およびキャリアガスとともに加熱炉を備えている反応管に注入して、カーボンナノチューブの連続集合体であるカーボンナノチューブ繊維を製造する方法において、
反応管入口と加熱炉入口との間の領域において、グラスホフ数(Gr)とレイノルズ数(Re)から算出されるGr/Re2値が0.12以下になるように調節することにより、回転流動を抑制することを特徴とする、カーボンナノチューブ繊維の製造方法。 - 前記反応管入口と加熱炉入口との間の温度勾配を調節して、グラスホフ数(Gr)とレイノルズ数(Re)が0.007≦Gr/Re2≦0.12を満足するようにするものである、請求項1に記載のカーボンナノチューブ繊維の製造方法。
- 前記反応管の反応領域は、1000〜3000℃に加熱され、前記反応管入口と加熱炉入口との温度差は510〜1000℃である、請求項1に記載のカーボンナノチューブ繊維の製造方法。
- 前記キャリアガスが、水素ガス、アンモニアガス、またはこれらの混合ガスを含む還元ガスを含むものである、請求項1に記載のカーボンナノチューブ繊維の製造方法。
- 前記キャリアガスが不活性ガスをさらに含むものである、請求項1に記載のカーボンナノチューブ繊維の製造方法。
- 前記炭素源が、メタン、エチレン、アセチレン、メチルアセチレン、ビニルアセチレン、エタノール、メタノール、プロパノール、アセトン、キシレン、クロロホルム、エチル酢酸、ジエチルエーテル、ポリエチレングリコール、ギ酸エチル、メシチレン、テトラヒドロフラン(THF)、ジメチルホルムアミド(DMF)、ジクロロメタン、ヘキサン、ベンゼン、四塩化炭素、およびペンタンからなる群より選択された一つ以上を含むものである、請求項1に記載のカーボンナノチューブ繊維の製造方法。
- 前記触媒または触媒前駆体が、鉄、ニッケル、コバルト、白金、ルテニウム、モリブデン、バナジウムおよびそれらの酸化物からなる群より選択される1つ以上を含むものである、請求項1に記載のカーボンナノチューブ繊維の製造方法。
- 前記触媒または触媒前駆体とともに、硫黄元素、硫黄含有化合物およびこれらの組み合わせから選択されるものを触媒活性剤としてさらに注入することである、請求項1に記載のカーボンナノチューブ繊維の製造方法。
- 前記触媒活性剤がメチルチオール、メチルエチルスルフィド、ジメチルチオケトン、フェニルチオール、ジフェニルスルフィド、ピリジン、キノリン、ベンゾチオフェン、チオフェン、およびこれらの組み合わせから選択される化合物を含むものである、請求項8に記載のカーボンナノチューブ繊維の製造方法。
- 前記触媒または触媒前駆体がメタロセン型であるものである、請求項1に記載のカーボンナノチューブ繊維の製造方法。
- 前記反応ガスのGHSV(Gas Hourly Space Velocity)が0.12〜6hr−1の範囲、前記キャリアガスのGHSVが1.2〜60hr−1の範囲で選択されるものである、請求項1に記載のカーボンナノチューブ繊維の製造方法。
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