JP3136334B2 - Method for producing carbon nanotube - Google Patents
Method for producing carbon nanotubeInfo
- Publication number
- JP3136334B2 JP3136334B2 JP09214164A JP21416497A JP3136334B2 JP 3136334 B2 JP3136334 B2 JP 3136334B2 JP 09214164 A JP09214164 A JP 09214164A JP 21416497 A JP21416497 A JP 21416497A JP 3136334 B2 JP3136334 B2 JP 3136334B2
- Authority
- JP
- Japan
- Prior art keywords
- present
- carbon nanotube
- organic compound
- producing carbon
- carbon nanotubes
- 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.)
- Expired - Lifetime
Links
Description
【０００１】[0001]
【発明の属する技術分野】本発明はカーボンナノチュー
ブの製造方法に関するものである。[0001] The present invention relates to a method for producing carbon nanotubes.
【０００２】[0002]
【従来の技術】カーボンナノチューブを製造する方法と
しては、アークプラズマ法及びＣＶＤによる方法が知ら
れている。アークプラズマ法は、真空中又は不活性気体
雰囲気中で炭素棒を電極とし、高電圧・高電流のアーク
放電を行い、カーボンナノチューブを製造するものであ
り、カーボンナノチューブは陰極堆積物中にグラファイ
ト、カーボンナノパーティクルなどと一緒に得られる。
ＣＶＤによる方法は、鉄、ニッケルなどの金属微粒子の
存在下で原料ガスを数百度で反応させて、カーボンナノ
チューブを製造するものである。この場合、原料ガスと
しては、ベンゼン、トルエン、オルトメチルジアリルケ
トン、アセチレン等が用いられる。2. Description of the Related Art As a method for producing carbon nanotubes, an arc plasma method and a method using CVD are known. In the arc plasma method, a carbon rod is used as an electrode in a vacuum or an inert gas atmosphere to perform high-voltage, high-current arc discharge to produce carbon nanotubes. Obtained together with carbon nanoparticles.
The CVD method involves producing a carbon nanotube by reacting a raw material gas at a temperature of several hundred degrees in the presence of fine metal particles such as iron and nickel. In this case, benzene, toluene, orthomethyldiallyl ketone, acetylene, or the like is used as a source gas.
【０００３】しかしながら、上記従来方法では、真空排
気装置や高電圧・大電流電源などの高価かつ危険な装置
を必要とするという問題があった。[0003] However, the above-mentioned conventional method has a problem that expensive and dangerous devices such as a vacuum exhaust device and a high-voltage / high-current power supply are required.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、高価かつ危
険な装置を用いないで、安価かつ安全にカーボンナノチ
ューブを製造する方法を提供することをその課題とす
る。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing carbon nanotubes inexpensively and safely without using expensive and dangerous equipment.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究を重ねた結果、本発明を完成する
に至った。即ち、本発明によれば、金属又は金属化合物
から選ばれる有機化合物の炭化促進固体触媒の粒子又は
粉末を加えた液状有機化合物に超音波を照射することか
らなるカーボンナノチューブの製造方法が提供される。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, a metal or metal compound
Particles of a solid catalyst for promoting carbonization of an organic compound selected from
Is ultrasonic irradiation applied to powdered liquid organic compounds?
The present invention provides a method for producing carbon nanotubes .
【０００６】以下、本発明について詳述する。本発明の
方法は、金属又は金属化合物から選ばれる固体触媒の粒
子又は粉末を加えた液状有機化合物に超音波を照射する
ことにより、カーボンナノチューブを製造することを特
徴とするものである。本明細書において「液状有機化合
物」とは室温で液体状態にある有機化合物のことをい
う。本発明において使用する液状有機化合物は特に限定
されないが、１分子中に含まれる水素原子と炭素原子と
の比Ｈ／Ｃが０．５〜２．５、好ましくは０．８〜１．
５の範囲にあるものである。このような有機化合物に
は、脂肪族系及び芳香族系のものが包含されるが、好ま
しくは芳香族系のものである。芳香族系有機化合物とし
ては、ベンゼン、トルエン、キシレン等のベンゼン系炭
化水素；クロロベンゼン、ジクロロベンゼン（ｏ−、ｍ
−及び／又はｐ−ジクロロベンゼン）、トリクロロベン
ゼン、ブロモベンゼン、ジブロモベンゼン等のハロゲン
化ベンゼン；メチルナフタレン、ジメチルナフタレン等
のナフタレン系化合物、コールタール等が挙げられる。
本発明において用いる固体触媒は、有機化合物の炭化を
促進させる作用を有する金属又は金属化合物からなるも
のである。一般的には、金属として、Ａｌ，Ｔｉ，Ｖ，
Ｃｒ，Ｍｎ，Ｆｅ，Ｎｉ，Ｃｏ，Ｃｕ，Ｚｎ，Ｚｒ，Ｍ
ｏ，Ｒｕ，Ｒｈ，Ｐｄ，Ａｇ，Ｃｄ，Ｉｎ，Ｓｎ，Ｓ
ｂ，Ｗ，Ｒｅ，Ｏｓ，Ｉｒ，Ｐｔ等が挙げられる。ま
た、それらの金属の化合物としては、酸化物、水酸化物
の他、硝酸塩、硫酸鉛、ハロゲン化物、（塩化物、臭化
物等）等が挙げられる。特に、ハロゲン化金属の使用が
好ましい。好ましいハロゲン化金属としては、塩化亜
鉛、塩化アルミニウム、塩化スズ、塩化ニッケル、塩化
鉄等が挙げられる。本発明で用いる前記固体触媒は粒子
状又は粉末状で用いられ、その平均粒径は０．１〜１０
００μｍ、好ましくは１〜１０μｍである。本発明にお
いて、有機化合物に対する固体触媒の添加量は、有機化
合物１００重量部に対して０．１〜３０重量部、好まし
くは０．５〜５重量部である。Hereinafter, the present invention will be described in detail. The method of the present invention comprises the steps of:
The method is characterized in that carbon nanotubes are produced by irradiating ultrasonic waves to liquid organic compounds to which particles or powders have been added. As used herein, the term "liquid organic compound" refers to an organic compound that is in a liquid state at room temperature. The liquid organic compound used in the present invention is not particularly limited, but the ratio H / C of hydrogen atoms to carbon atoms contained in one molecule is 0.5 to 2.5, preferably 0.8 to 1.
5 in the range. Such organic compounds include aliphatic ones and aromatic ones, but are preferably aromatic ones. Examples of the aromatic organic compound include benzene-based hydrocarbons such as benzene, toluene, and xylene; chlorobenzene, dichlorobenzene (o-, m-
-And / or p-dichlorobenzene), halogenated benzenes such as trichlorobenzene, bromobenzene and dibromobenzene; naphthalene-based compounds such as methylnaphthalene and dimethylnaphthalene; and coal tar.
The solid catalyst used in the present invention is used for carbonizing an organic compound.
It is also composed of a metal or metal compound having an accelerating action.
It is. Generally, Al, Ti, V,
Cr, Mn, Fe, Ni, Co, Cu, Zn, Zr, M
o, Ru, Rh, Pd, Ag, Cd, In, Sn, S
b, W, Re, Os, Ir, Pt and the like. Ma
And, as the compound of these metals, oxides, other hydroxides, nitrates, lead sulfate, halide, and the like (chloride, bromide, etc.). In particular, the use of a metal halide is preferred. Preferred metal halides include zinc chloride, aluminum chloride, tin chloride, nickel chloride, iron chloride and the like. The solid catalyst used in the present invention is a particle
Used in the form of a powder or powder, having an average particle size of 0.1 to 10
00 μm, preferably 1 to 10 μm. In the present invention, the amount of the solid catalyst to be added to the organic compound is 0.1 to 30 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the organic compound.
【０００７】本発明において使用する超音波において、
その周波数は１０〜１０００ｋＨｚ、好ましくは１５〜
２５ｋＨｚであり、その単位時間当りの投入エネルギー
は１０〜２０００Ｗ、好ましくは５００〜１０００Ｗで
あり、投入時間は１〜３０分程度である。本発明におい
ては、反応液の温度上昇によりその反応性を低下させな
いように、反応液を冷却させながら、上記超音波の投入
を行うことが望ましい。一般的には、反応液の温度は−
２０〜１００℃、好ましくは１０〜３０℃に保持するの
がよい。また、反応をより効果的に起こすため、反応液
中にアルゴン等の不活性ガスをバブリングさせながら、
上記超音波の投入を行うことが望ましい。[0007] In the ultrasonic wave used in the present invention,
Its frequency is 10 to 1000 kHz, preferably 15 to
25 kHz, the input energy per unit time is 10 to 2000 W, preferably 500 to 1000 W, and the input time is about 1 to 30 minutes. In the present invention, it is desirable to carry out the above-mentioned ultrasonic wave while cooling the reaction solution so that the reactivity of the reaction solution does not decrease due to a rise in the temperature of the reaction solution. Generally, the temperature of the reaction solution is-
The temperature should be maintained at 20 to 100 ° C, preferably 10 to 30 ° C. In order to make the reaction more effective, while bubbling an inert gas such as argon into the reaction solution,
It is desirable that the above-mentioned ultrasonic wave be input.
【０００８】[0008]
【実施例】次に本発明を実施例により詳述する。Next, the present invention will be described in detail with reference to examples.
【０００９】実施例１ 原料液体としてｏ−ジクロロベンゼン５０ｍｌを使用
し、これに固体触媒としてニッケル０．５ｇ（平均粒径
１０μｍ）を添加した。この固体触媒を添加した原料液
体に超音波を周波数２０ｋＨｚ、単位時間当りの投入エ
ネルギー６００Ｗの条件で２分３０秒間加えた。反応液
は、温度上昇防止のため氷水で冷却し、その温度を２０
℃以下に保持した。また反応性を向上させるため反応液
中にアルゴンガスをバブリングさせた。そして反応直後
の反応液から固形浮遊物を採取し、透過型電子顕微鏡で
観察した結果、カーボンナノチューブの生成を確認し
た。Example 1 50 ml of o-dichlorobenzene was used as a raw material liquid, and 0.5 g of nickel (average particle size: 10 μm) was added as a solid catalyst. Ultrasonic waves were applied to the raw material liquid to which the solid catalyst was added at a frequency of 20 kHz and an input energy of 600 W per unit time for 2 minutes and 30 seconds. The reaction solution is cooled with ice water to prevent the temperature from rising.
C. or less. In order to improve the reactivity, argon gas was bubbled into the reaction solution. Then, a solid suspended matter was collected from the reaction solution immediately after the reaction, and observed by a transmission electron microscope. As a result, generation of carbon nanotubes was confirmed.
【００１０】実施例２ 実施例１において、固体触媒としてニッケル の代わり
に塩化亜鉛０．５ｇ（平均粒径１００μｍ）を用いた以
外は同様な操作を行った。そして反応直後の反応液から
固形浮遊物を採取し、透過型電子顕微鏡で観察した結
果、カーボンナノチューブの生成を確認した。本実施例
では実施例１の場合より、カーボンナノチューブの生成
量が多く確認できた。Example 2 The same operation as in Example 1 was carried out except that 0.5 g of zinc chloride (average particle size: 100 μm) was used instead of nickel as the solid catalyst. Then, a solid suspended matter was collected from the reaction solution immediately after the reaction, and observed by a transmission electron microscope. As a result, generation of carbon nanotubes was confirmed. In this example, a larger amount of carbon nanotubes was produced than in Example 1.
【００１１】比較例 実施例１において固体触媒を用いないで同様な操作を行
った。その結果、結晶性の固体生成物は得られなかっ
た。Comparative Example A similar operation was performed in Example 1 without using a solid catalyst. As a result, a crystalline solid product was not obtained.
【００１２】[0012]
【発明の効果】本発明によれば、超音波を利用する手法
を採用したので、従来方法で用いたような高価かつ危険
な装置を用いる必要がなく、安価かつ安全にカーボンナ
ノチューブを製造することが可能となる。According to the present invention, since a method utilizing ultrasonic waves is employed, it is not necessary to use expensive and dangerous equipment used in the conventional method, and it is possible to manufacture carbon nanotubes inexpensively and safely. Becomes possible.
フロントページの続き (72)発明者 湯村 守雄 茨城県つくば市東１丁目１番 工業技術 院物質工学工業技術研究所内 (72)発明者 伊ヶ崎 文和 茨城県つくば市東１丁目１番 工業技術 院物質工学工業技術研究所内 (72)発明者 藤原 修三 茨城県つくば市東１丁目１番 工業技術 院物質工学工業技術研究所内 (56)参考文献 特開 平９−31757（ＪＰ，Ａ) 高圧力の科学と技術６［３］（1997) ｐ．159−166 化学と工業50［９］（1997）ｐ．1366 −1368 日本産業技術振興会技術資料270 （1997−10−24）ｐ．143−144 (58)調査した分野(Int.Cl.7，ＤＢ名) C01B 31/02 101 B01J 19/10 B01J 23/06 B01J 23/755 D01F 9/127 ＣＡ（ＳＴＮ)Continued on the front page (72) Inventor Morio Yumura 1-1-1, Higashi, Tsukuba, Ibaraki Pref., National Institute of Advanced Industrial Science and Technology (72) Inventor Fumikazu Igasaki 1-1-1, Higashi, Tsukuba, Ibaraki Pref. Inside the Technical Research Institute (72) Inventor Shuzo Fujiwara 1-1 1-1 Higashi, Tsukuba-shi, Ibaraki Pref. National Institute of Advanced Industrial Science and Technology (56) References [3] (1997) p. 159-166 Chemistry and Industry 50 [9] (1997) p. 1366-1368 Japan Society for Industrial Technology Promotion Technical Data 270 (1997-10-24) p. 143-144 (58) Field surveyed (Int. Cl. 7 , DB name) C01B 31/02 101 B01J 19/10 B01J 23/06 B01J 23/755 D01F 9/127 CA (STN)
Claims (2)
物の炭化促進固体触媒の粒子又は粉末を加えた液状有機
化合物に超音波を照射することからなるカーボンナノチ
ューブの製造方法。 An organic compound selected from the group consisting of metals and metal compounds.
Organic matter to which solid catalyst particles or powder are added
A carbon nanotube consisting of irradiating a compound with ultrasonic waves
Method of manufacturing tube.
いる請求項１の方法。 2. An aromatic compound is used as the liquid organic compound.
The method of claim 1, wherein
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09214164A JP3136334B2 (en) | 1997-07-23 | 1997-07-23 | Method for producing carbon nanotube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09214164A JP3136334B2 (en) | 1997-07-23 | 1997-07-23 | Method for producing carbon nanotube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1143316A JPH1143316A (en) | 1999-02-16 |
| JP3136334B2 true JP3136334B2 (en) | 2001-02-19 |
Family
ID=16651302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09214164A Expired - Lifetime JP3136334B2 (en) | 1997-07-23 | 1997-07-23 | Method for producing carbon nanotube |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3136334B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857217B (en) * | 2009-04-07 | 2013-03-20 | 清华大学 | Carbon nano tube metal composite and preparation method thereof |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100372332B1 (en) * | 1999-06-11 | 2003-02-17 | 일진나노텍 주식회사 | Massive synthesis method of purified carbon nanotubes vertically aligned on large-area substrate using the thermal chemical vapor deposition |
| KR100376197B1 (en) * | 1999-06-15 | 2003-03-15 | 일진나노텍 주식회사 | Low temperature synthesis of carbon nanotubes using metal catalyst layer for decompsing carbon source gas |
| KR100335384B1 (en) * | 1999-06-21 | 2002-05-06 | 최규술 | A method for fabrication of carbon nanotube in multi-step anodized alumina template and an electron emission apparatus using the carbon nanotube fabricated by this method |
| KR19990073589A (en) * | 1999-07-27 | 1999-10-05 | 이철진 | Massive synthesis of carbon nanotubes using low pressure chemical vapor deposition. |
| US6706402B2 (en) * | 2001-07-25 | 2004-03-16 | Nantero, Inc. | Nanotube films and articles |
| KR100571803B1 (en) * | 2002-05-03 | 2006-04-17 | 삼성전자주식회사 | Semiconductor carbon nano tube functionalized by hydrogen, electronic device and method of fabrication thereof |
| JP4674304B2 (en) * | 2003-09-30 | 2011-04-20 | 国立大学法人愛媛大学 | Method and apparatus for producing carbon nanotube |
| KR100657913B1 (en) | 2004-11-20 | 2006-12-14 | 삼성전자주식회사 | method of synthesizing single-wall carbon nanotube at room temperature and atmosphere pressure |
| JP4899045B2 (en) * | 2005-03-01 | 2012-03-21 | 国立大学法人東北大学 | Nanocarbon material generation method, generation apparatus, and nanocarbon material |
| JP5272136B2 (en) * | 2007-04-09 | 2013-08-28 | 富山県 | Method for producing nanocarbon material |
| CN102527695A (en) * | 2012-01-05 | 2012-07-04 | 中国科学院生态环境研究中心 | Method for preparing nano iron/carbon compound material by kitchen waste |
| JP5845515B2 (en) * | 2012-01-16 | 2016-01-20 | 東洋インキＳｃホールディングス株式会社 | Method for producing catalyst for carbon nanotube synthesis, method for producing aggregate of carbon nanotubes using the same, and aggregate of carbon nanotubes |
-
1997
- 1997-07-23 JP JP09214164A patent/JP3136334B2/en not_active Expired - Lifetime
Non-Patent Citations (3)
| Title |
|---|
| 化学と工業５０［９］（１９９７）ｐ．１３６６−１３６８ |
| 日本産業技術振興会技術資料２７０（１９９７−１０−２４）ｐ．１４３−１４４ |
| 高圧力の科学と技術６［３］（１９９７）ｐ．１５９−１６６ |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857217B (en) * | 2009-04-07 | 2013-03-20 | 清华大学 | Carbon nano tube metal composite and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH1143316A (en) | 1999-02-16 |
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