JP2001019413A - Production of carbon nanofiber and device therefor - Google Patents
Production of carbon nanofiber and device thereforInfo
- Publication number
- JP2001019413A JP2001019413A JP11222878A JP22287899A JP2001019413A JP 2001019413 A JP2001019413 A JP 2001019413A JP 11222878 A JP11222878 A JP 11222878A JP 22287899 A JP22287899 A JP 22287899A JP 2001019413 A JP2001019413 A JP 2001019413A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- magnetic separator
- magnetic
- metal catalyst
- valve
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、水素吸蔵材など
に用いられるカーボンナノファイバーの製造方法及び装
置に係わる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for producing carbon nanofibers used as a hydrogen storage material.
【０００２】[0002]
【従来の技術】金属触媒を用いてエチレンなどのハイド
ロカーボンガスや一酸化炭素などを熱分解して得られる
カーボンナノファイバーが、最近水素吸蔵合金以上に水
素ガスを吸蔵するという驚異的な実験結果が発表され、
水素貯蔵材料として注目されている。この水素吸蔵のメ
カニズムは完全に明らかにされてはいないが、水素吸蔵
合金は比重が重く繰り返し使用で粉化するなどの欠点が
あるので、合金と同等以上の貯蔵性能が安定的に証明さ
れれば、燃料電池などの水素貯蔵材料として活用できる
ので、現在各所でその性能が追試されている。2. Description of the Related Art A phenomenal experimental result that carbon nanofibers obtained by thermally decomposing a hydrocarbon gas such as ethylene or carbon monoxide using a metal catalyst can absorb hydrogen gas more recently than a hydrogen storage alloy. Was announced,
It is attracting attention as a hydrogen storage material. Although the mechanism of hydrogen storage has not been fully elucidated, hydrogen storage alloys have the drawbacks of heavy specific gravity and powdering due to repeated use. For example, it can be used as a hydrogen storage material for fuel cells and the like.
【０００３】また、現在リチュームイオン二次電池の陰
極に使用されているカーボンのリチュームイオン吸蔵能
力は電池の容量を左右する重要な因子なので、この陰極
にカーボンナノファイバーを用いることによってリチュ
ームイオンの吸蔵能力を増やすことができれば、電池容
量の飛躍的向上が期待できる。[0003] Further, the capacity of carbon, which is currently used for the cathode of a lithium ion secondary battery, to absorb lithium, is an important factor influencing the capacity of the battery. If capacity can be increased, a dramatic improvement in battery capacity can be expected.
【０００４】しかしながらカーボンナノファイバーは熱
分解生成物なので、これ以外の構造を持ったカーボンや
ハイドロカーボンなどの好ましくない異物の生成・混在
は避けられない。これらの異物が混在することにより、
単位体積ないし単位重量当りの吸蔵容量は当然減少する
ので、純粋なカーボンナノファイバーが得られる製造プ
ロセスが必要になるが、従来そのようなプロセスは存在
しなかった。[0004] However, since carbon nanofibers are pyrolysis products, generation and mixing of undesirable foreign substances such as carbon and hydrocarbons having other structures cannot be avoided. By mixing these foreign substances,
Since the storage capacity per unit volume or unit weight is naturally reduced, a manufacturing process for obtaining pure carbon nanofibers is required, but such a process has not existed conventionally.
【０００５】[0005]
【発明が解決しようとする課題】以上に鑑みこの発明
は、好ましくない異物を含まず、単位体積ないし単位重
量当りの水素ガスやリチュームイオンなどの吸蔵能力の
高いカーボンナノファイバーの製造方法と装置を提供す
ることを目的とする。SUMMARY OF THE INVENTION In view of the above, the present invention provides a method and an apparatus for producing carbon nanofibers which do not contain undesired foreign substances and have a high storage capacity for hydrogen gas and lithium ions per unit volume or unit weight. The purpose is to provide.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するため
に、請求項１に記載の発明は、熱分解温度以上のキュー
リー温度を有する金属触媒すなわち熱分解温度以上の温
度で磁性を有するコバルト等の金属触媒を用いてエチレ
ンや一酸化炭素などを熱分解して得られる生成物を、ガ
ス循環過程において磁気分離機を通すことにより、該金
属触媒片を核として成長したカーボンナノファイバーを
磁力で分離することを特徴とする、カーボンナノファイ
バーの製造方法である。In order to achieve the above object, the present invention is directed to a metal catalyst having a Curie temperature higher than the thermal decomposition temperature, such as cobalt having a magnetism at a temperature higher than the thermal decomposition temperature. The product obtained by thermal decomposition of ethylene, carbon monoxide, etc. using a metal catalyst of the above is passed through a magnetic separator in the gas circulation process, so that the carbon nanofiber grown with the metal catalyst piece as a nucleus is magnetized. It is a method for producing carbon nanofibers, characterized by separating.
【０００７】また請求項２に記載の発明は、少なくとも
原料ガスの組成を調整するガス調整槽と、熱分解温度以
上の温度で磁性を有するコバルト等の金属触媒粒子を充
填した固定層及び／又は流動層で構成される熱分解反応
槽と、複数の磁気分離機と、ガスフィルターとを備える
と共に、ガス調整槽と熱分解反応槽と一方の磁気分離機
を繋ぐガス循環回路と、他方の磁気分離機とガスフィル
ターを繋ぐガス循環回路とをそれぞれ独立して構築し得
るようにしたことを特徴とする、カーボンナノファイバ
ーの製造装置である。[0007] The invention according to claim 2 provides a gas regulating tank for adjusting at least the composition of the raw material gas, a fixed layer filled with metal catalyst particles such as cobalt having magnetism at a temperature higher than the thermal decomposition temperature, and / or A pyrolysis reaction tank composed of a fluidized bed, a plurality of magnetic separators, a gas filter, and a gas circulation circuit that connects the gas adjustment tank, the pyrolysis reaction tank and one magnetic separator, and the other magnetic field A carbon nanofiber manufacturing apparatus characterized in that a gas circulation circuit connecting a separator and a gas filter can be constructed independently of each other.
【０００８】また請求項３に記載の発明は、ウール状の
金属触媒を充填するなどして金属触媒によって高勾配磁
場を形成した磁気分離機を用いることにより、磁気分離
機に触媒機能を持たせて前記熱分解反応槽を省略したこ
とを特徴とする、請求項２に記載のカーボンナノファイ
バーの製造装置である。According to a third aspect of the present invention, the magnetic separator has a catalytic function by using a magnetic separator in which a high gradient magnetic field is formed by the metal catalyst by, for example, filling a wool-like metal catalyst. The apparatus for producing carbon nanofibers according to claim 2, wherein the thermal decomposition reaction tank is omitted.
【０００９】[0009]
【発明の実施の形態】以下、本発明の実施の形態を実施
例にもとずき図面を参照して説明する。図１は実施例の
説明図、図２はカーボンナノファイバーの模式図、をそ
れぞれ示す。Embodiments of the present invention will be described below with reference to the drawings based on embodiments. FIG. 1 is an explanatory view of an example, and FIG. 2 is a schematic view of a carbon nanofiber.
【００１０】図２の模式図に示すようにカーボンナノフ
ァイバー３は、微細な金属触媒片１を核にして偏平な炭
素片２がほぼＧ＝０．３４ナノメートルの隙間をもって
成長した、太さＤ＝１０〜数百ナノメートル、長さＬ＝
数ミクロン，程度の微小な炭素繊維である。微細な金属
触媒片１の生成過程は、原料ガスが金属触媒と接触して
堆積した炭素が金属内に拡散し、金属に生成する炭化物
の体積変化に基ずく応力で触媒表面が破損崩壊して微粒
子になるものと推定されているが、いずれにせよ金属触
媒は微粒子となって消耗し、電子顕微鏡による観察結果
では、図２に示すような微細な金属触媒片１を核として
規則的な形態をもったカーボンナノファイバー３が形成
されている。As shown in the schematic diagram of FIG. 2, the carbon nanofibers 3 are formed by growing flat carbon pieces 2 with a gap of approximately G = 0.34 nm with the fine metal catalyst pieces 1 as nuclei. D = 10 to several hundred nanometers, length L =
It is a fine carbon fiber of several microns. The process of forming the fine metal catalyst pieces 1 is such that the raw material gas comes into contact with the metal catalyst, the deposited carbon diffuses into the metal, and the catalyst surface breaks and collapses due to stress based on the volume change of the carbide generated in the metal. It is presumed that the metal catalyst becomes fine particles, but in any case, the metal catalyst is consumed as fine particles, and the results of observation by an electron microscope show that the fine metal catalyst piece 1 as shown in FIG. Is formed.
【００１１】しかしながらカーボンナノファイバー３
は、エチレンなどのハイドロカーボンガスや一酸化炭素
などを５５０℃〜６００℃程度の比較的低温下で還元性
熱分解によって製造されるものであるから、これらの条
件においては目的とするカーボンナノファイバー以外の
形態のカーボンやハイドロカーボンなどの異物の同時生
成・混在を防止することは困難である。However, carbon nanofiber 3
Is produced by reductive pyrolysis of a hydrocarbon gas such as ethylene or carbon monoxide at a relatively low temperature of about 550 ° C. to 600 ° C., so that under these conditions, the target carbon nanofiber is produced. It is difficult to prevent simultaneous generation and mixing of foreign substances such as carbon and hydrocarbons in other forms.
【００１２】この装置は、このような異物をカーボンナ
ンノファイバーの生成過程において除去するもので、主
要素は図１に示すように、ガス調整槽４、熱分解反応槽
５、複数の磁気分離機６、６’、及びガスフィルター７
で構成されている。ガス調整槽４にはガスの組成と温度
を常に最適状態に維持せしめるために、内部に加熱器８
と冷却器９が、またエチレンなどのハイドロカーボンガ
スや一酸化炭素などの原料ガス１０の自動調整弁１１
と、還元用の水素ガス１２の自動調整弁１３が設けられ
ている。なお、加熱器８と冷却器９は熱分解反応槽５の
内部に設けることができることは勿論である。熱分解反
応槽５のガス分散板１４上には熱分解温度以上のキュー
リー温度（磁性喪失温度）を有する金属触媒粒子１５が
充填されており、磁気分離機６、６’はそれぞれ高勾配
磁場を形成するウール状金属１６とその回りに配した電
磁石１７とで構成されている。図中の１８、１９はガス
循環ブロワ、２０は熱分解で生成した非磁性物質すなわ
ち異物を示すが、異物２０の捕捉・排出装置などの図示
は省略されている。また、ガスフィルター７はフィルタ
ーを耐熱性繊維で構成する周知のバグフィルターの略図
を示し、フィルターで分離された固形微粒子すなわちカ
ーボンナノファイバー３の排出装置などの図示は省略さ
れている。This apparatus removes such foreign matters in the process of producing carbon nanofibers. The main elements are a gas regulating tank 4, a pyrolysis reaction tank 5, and a plurality of magnetic separators, as shown in FIG. 6, 6 'and gas filter 7
It is composed of A heater 8 is provided inside the gas regulating tank 4 in order to keep the composition and temperature of the gas in an optimum state at all times.
And a cooler 9, and an automatic regulating valve 11 for a raw material gas 10 such as a hydrocarbon gas such as ethylene or carbon monoxide.
And an automatic regulating valve 13 for hydrogen gas 12 for reduction. Note that the heater 8 and the cooler 9 can be provided inside the thermal decomposition reaction tank 5 as a matter of course. Metal catalyst particles 15 having a Curie temperature (magnetism loss temperature) equal to or higher than the thermal decomposition temperature are filled on the gas dispersion plate 14 of the thermal decomposition reaction tank 5, and the magnetic separators 6 and 6 'each apply a high gradient magnetic field. It is composed of a wool-like metal 16 to be formed and an electromagnet 17 arranged around the metal. In the figure, reference numerals 18 and 19 denote gas circulation blowers, and reference numeral 20 denotes a non-magnetic substance, that is, foreign matter generated by thermal decomposition, but illustration of a device for capturing and discharging the foreign matter 20 is omitted. The gas filter 7 is a schematic diagram of a well-known bag filter in which the filter is made of a heat-resistant fiber, and a device for discharging solid fine particles separated by the filter, that is, a carbon nanofiber 3 is not shown.
【００１３】以上の構成において、以下に操作方法を説
明する。起動時は自動調整弁１３を開いて系内に水素ガ
ス１２を導入し、金属触媒粒子１５を含め系内を還元状
態に維持する。次いで自動調整弁１１を開きハイドロカ
ーボンガスや一酸化炭素などの原料ガス１０を導入す
る。熱分解の進行に伴ってガス調整槽４内のガス組成は
常に変化するので、自動調整弁１１、１３によりガス組
成を最適値に維持するように自動調整すると共に、加熱
器８及び／又は冷却器９によってガスの温度を最適熱分
解温度（例えば６００℃）に調整する。調整槽４内で調
整された原料ガスは、熱分解反応槽５のガス分散板１４
を経て、金属触媒粒子１５で形成される固定層及び／又
は流動層に接触して反応し、ここで金属触媒粒子１５の
表面が崩壊して生ずる金属触媒片１を核としてカーボン
ナノファイバー３が成長する。In the above configuration, an operation method will be described below. At the time of startup, the automatic regulating valve 13 is opened to introduce the hydrogen gas 12 into the system, and the system including the metal catalyst particles 15 is maintained in a reduced state. Next, the automatic regulating valve 11 is opened, and the raw material gas 10 such as hydrocarbon gas or carbon monoxide is introduced. Since the gas composition in the gas regulating tank 4 constantly changes with the progress of the thermal decomposition, the gas regulating composition is automatically adjusted by the automatic regulating valves 11 and 13 so as to maintain the gas composition at the optimum value, and the heater 8 and / or the cooling unit are cooled. The temperature of the gas is adjusted to the optimum pyrolysis temperature (for example, 600 ° C.) by the vessel 9. The raw material gas adjusted in the adjustment tank 4 is supplied to the gas dispersion plate 14 of the pyrolysis reaction tank 5.
The carbon nanofibers 3 are formed by contacting and reacting with the fixed layer and / or the fluidized bed formed of the metal catalyst particles 15, where the metal catalyst pieces 1 generated by the collapse of the surface of the metal catalyst particles 15 are used as nuclei. grow up.
【００１４】上記の成長過程において適宜時間を経過
後、ガス循環ブロワー１８の回転数を切替えてガス流速
を上げ金属触媒粒子１５を流動化せしめることにより、
成長したカーボンナノファイバーはガス中に浮遊し磁気
分離機６で捕捉される。非磁性体すなわち異物２０は磁
気分離機６を通過してガス調整槽４から排除される。な
お、金属触媒粒子１５は通常は固定層とするが、カーボ
ンナノファイバーの成長を妨げぬ範囲で微弱な流動層と
してもよい。After a suitable time has elapsed in the above-mentioned growth process, the number of revolutions of the gas circulation blower 18 is switched to increase the gas flow rate to fluidize the metal catalyst particles 15.
The grown carbon nanofibers float in the gas and are captured by the magnetic separator 6. The non-magnetic substance, that is, the foreign matter 20 passes through the magnetic separator 6 and is removed from the gas regulating tank 4. The metal catalyst particles 15 are usually a fixed bed, but may be a weak fluidized bed as long as the growth of carbon nanofibers is not hindered.
【００１５】しかして、磁気分離機６、６’の入出口に
は図示のような配置で、Ａ，Ｂ，Ｃ，Ｄ，Ｅ，Ｆ，Ｇ，
Ｈの８個の切替え弁が設けられている。説明を分かり易
くするため、図示例においては閉状態の弁は黒塗してあ
る。すなわち図示例のように、弁Ａ，Ｄ，Ｅ，Ｈを開、
弁Ｂ，Ｃ，Ｆ、Ｇを閉とすることにより、ガス調整槽
４、熱分解反応槽５、弁Ａ，磁気分離機６、弁Ｅを繋ぐ
閉回路において、原料ガスの循環によるカーボンナノフ
ァイバーの生成ならびに磁気分離機６における磁気吸着
が行われる。また、磁気分離機６’、弁Ｈ、ガスフィル
ター７、弁Ｄを繋ぐ閉回路においては、磁気分離機６’
を脱磁してウール状金属１６に磁気吸着されているカー
ボンナノファイバーを解放してガス中に浮遊せしめ、こ
れをガスフィルター７で捕捉、回収する。一定時間経過
してカーボンナノファイバーの生成ならびに回収サイク
ルが完了後、各切替え弁の開閉を逆にして磁気分離機
６、６’を切替えることにより同様な運転が連続的に繰
り返される。However, the inlets and outlets of the magnetic separators 6 and 6 'are arranged as shown in the figure, and A, B, C, D, E, F, G,
H eight switching valves are provided. In the illustrated example, the valve in the closed state is painted black for easy understanding. That is, the valves A, D, E, and H are opened as shown in the illustrated example,
By closing the valves B, C, F, and G, the carbon nanofibers are circulated by circulating the raw material gas in a closed circuit connecting the gas regulating tank 4, the pyrolysis reaction tank 5, the valve A, the magnetic separator 6, and the valve E. And magnetic adsorption in the magnetic separator 6 are performed. In a closed circuit connecting the magnetic separator 6 ', the valve H, the gas filter 7, and the valve D, the magnetic separator 6'
Is demagnetized to release the carbon nanofibers magnetically adsorbed to the wool-like metal 16 to float in the gas, which is captured and recovered by the gas filter 7. After a certain period of time has elapsed and the generation and recovery cycle of the carbon nanofibers is completed, the same operation is continuously repeated by switching the magnetic separators 6 and 6 'by reversing the opening and closing of each switching valve.
【００１６】前記のように、磁気分離機６、６’は高勾
配磁場を形成するウール状金属１６とその回りに配した
電磁石１７とで構成されているが、ウール状金属１６の
材質を触媒金属と同じにすると共に線径を小さくして比
表面積を増やすことにより、触媒機能を持たせて前記の
熱分解反応槽４を省略し、装置を簡略化することもでき
る。As described above, the magnetic separators 6 and 6 'are composed of the wool-like metal 16 forming a high gradient magnetic field and the electromagnet 17 disposed therearound. By increasing the specific surface area by reducing the wire diameter to the same as that of the metal, the thermal decomposition reaction tank 4 can be omitted by providing a catalytic function, and the apparatus can be simplified.
【００１７】[0017]
【発明の効果】本発明は、以上説明したように構成され
ているので、以下に記載されるような効果を奏する。Since the present invention is configured as described above, it has the following effects.
【００１８】熱分解温度において磁性を有するコバルト
などの金属を核として形成されるカーボンナノファイバ
ーのみが選択的に製造され、従来不可能だった異物除去
が可能となる。したがって本発明によって製造されたカ
ーボンナノファイバーは異物を含まないので、単位体積
ないし単位重量当りの水素ガスやリチュームイオンの吸
蔵能力が高くなり、燃料電池の水素貯蔵材料やリチュー
ムイオン二次電池の陰極材料など、付加価値の高い工業
材料として利用できる。[0018] Only carbon nanofibers formed by using a metal such as cobalt having magnetic properties at the pyrolysis temperature as a nucleus are selectively produced, thereby enabling foreign matter removal which has been impossible in the past. Therefore, the carbon nanofibers manufactured according to the present invention do not contain foreign matter, so that the hydrogen gas or lithium ion storage capacity per unit volume or unit weight is increased, and the hydrogen storage material of a fuel cell and the cathode of a lithium ion secondary battery are increased. It can be used as high value-added industrial materials such as materials.
【図１】本発明の実施例の説明図である。FIG. 1 is an explanatory diagram of an embodiment of the present invention.
【図２】カーボンナノファイバーの模式図である。FIG. 2 is a schematic view of a carbon nanofiber.
１ 金属触媒片 ２ 炭素片 ３ カーボンナノファイバー ４ ガス調整槽 ５ 熱分解反応槽 ６、６’ 磁気分離機 ７ ガスフィルター １０ 原料ガス １１、１３ 自動調整弁 １５ 金属触媒粒子 １６ ウール状金属 １７ 電磁石 ２０ 異物 DESCRIPTION OF SYMBOLS 1 Metal catalyst piece 2 Carbon piece 3 Carbon nanofiber 4 Gas adjustment tank 5 Pyrolysis reaction tank 6, 6 'Magnetic separator 7 Gas filter 10 Raw material gas 11, 13 Automatic adjustment valve 15 Metal catalyst particles 16 Wool-like metal 17 Electromagnet 20 Foreign matter
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【手続補正書】[Procedure amendment]
【提出日】平成１２年５月２６日（２０００．５．２
６）[Submission date] May 26, 2000 (2005.2.
6)
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】特許請求の範囲[Correction target item name] Claims
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【特許請求の範囲】[Claims]
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００８[Correction target item name] 0008
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００８】また請求項３に記載の発明は、少なくとも
原料ガスの組成を調整するガス調整槽と、熱分解温度以
上の温度で磁性を有するコバルト等のウール状金属触媒
を充填して高勾配磁場を形成した複数の磁気分離機と、
ガスフィルターとを備えると共に、ガス調整槽と一方の
磁気分離機を繋ぐガス循環回路と、他方の磁気分離機と
ガスフィルターを繋ぐガス循環回路とをそれぞれ独立し
て構築し得るようにしたことを特徴とする、カーボンナ
ノファイバーの製造装置である。[0008] Further, the invention according to claim 3 has at least
A gas regulating tank for adjusting the composition of the raw material gas
Woollike metal catalysts such as cobalt that are magnetic at high temperatures
A plurality of magnetic separators filled with to form a high gradient magnetic field,
In addition to having a gas filter,
Gas circulation circuit connecting the magnetic separator and the other magnetic separator
Independent gas circulation circuits connecting gas filters
An apparatus for producing carbon nanofibers , characterized in that the apparatus can be constructed by performing the following steps .
Claims (3)
バルト等の金属触媒を用いてエチレンや一酸化炭素など
を熱分解して得られる生成物を、ガス循環過程において
磁気分離機を通すことにより、該金属触媒片を核として
成長したカーボンナノファイバーを磁力で分離すること
を特徴とする、カーボンナノファイバーの製造方法。A product obtained by thermally decomposing ethylene, carbon monoxide or the like using a metal catalyst such as cobalt having a magnetism at a temperature higher than the thermal decomposition temperature is passed through a magnetic separator in a gas circulation process. Wherein the carbon nanofiber grown with the metal catalyst piece as a nucleus is separated by magnetic force.
ス調整槽と、熱分解温度以上の温度で磁性を有するコバ
ルト等の金属触媒粒子を充填した固定層及び／又は流動
層で構成される熱分解反応槽と、複数の磁気分離機と、
ガスフィルターとを備えると共に、ガス調整槽と熱分解
反応槽と一方の磁気分離機を繋ぐガス循環回路と、他方
の磁気分離機とガスフィルターを繋ぐガス循環回路とを
それぞれ独立して構築し得るようにしたことを特徴とす
る、カーボンナノファイバーの製造装置。2. Pyrolysis comprising at least a gas adjusting tank for adjusting the composition of a raw material gas, and a fixed bed and / or a fluidized bed filled with metal catalyst particles such as cobalt having magnetism at a temperature not lower than the pyrolysis temperature. A reaction vessel, a plurality of magnetic separators,
In addition to having a gas filter, a gas circulation circuit connecting the gas conditioning tank, the pyrolysis reaction tank and one magnetic separator, and a gas circulation circuit connecting the other magnetic separator and the gas filter can be independently constructed. An apparatus for producing carbon nanofibers, characterized in that:
金属触媒によって高勾配磁場を形成した磁気分離機を用
いることにより、磁気分離機に触媒機能を持たせて前記
熱分解反応槽を省略したことを特徴とする、請求項２に
記載のカーボンナノファイバーの製造装置。3. The use of a magnetic separator in which a high gradient magnetic field is formed by a metal catalyst by filling a wool-like metal catalyst or the like, so that the magnetic separator has a catalytic function and the thermal decomposition reaction tank is omitted. The apparatus for producing carbon nanofibers according to claim 2, wherein:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11222878A JP3100962B1 (en) | 1999-07-01 | 1999-07-01 | Method and apparatus for producing carbon nanofiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11222878A JP3100962B1 (en) | 1999-07-01 | 1999-07-01 | Method and apparatus for producing carbon nanofiber |
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| Publication Number | Publication Date |
|---|---|
| JP3100962B1 JP3100962B1 (en) | 2000-10-23 |
| JP2001019413A true JP2001019413A (en) | 2001-01-23 |
Family
ID=16789311
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11222878A Expired - Fee Related JP3100962B1 (en) | 1999-07-01 | 1999-07-01 | Method and apparatus for producing carbon nanofiber |
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| Country | Link |
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| JP (1) | JP3100962B1 (en) |
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