1311544 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關於碳奈米管等之氣相長成碳纖維的高效 率製造方法。 【先前技術】 以氣相長成法製得之碳纖維（氣相長成碳纖維）因可 比較容易製得高長寬比之碳纖維，向來有活躍之硏究，有 關製造方法之報導亦所在多有。近年來，尤受矚目之碳奈 米管（亦即纖維經奈米層級之碳纖維）亦可應用該氣相長 成法合成。 第1圖係以氣相長成法連續製造碳纖維之反應裝置的 —例之示意圖。舉一般製造方法之一例，原料烴係用C0 、甲烷、乙炔、乙烯、苯、甲苯等。原料烴在常溫係氣態 者，於氣態與載氣混合供給，液態者則氣化後與載氣混合 供給，或液態下於加熱區域噴霧。載氣係用惰性氣體氮氣 ’還原性之氫氣等。有時係供給烴於經真空減壓之系統內 。觸媒係用，載持金屬於氧化鋁等載體之載持型觸媒，雙 (7? 5 -環戊二烯）鐵等有機金屬化合物。使用載持型觸 媒時，係將載持型觸媒預先設置於反應區加熱進行必要之 前處理後供給原料烴使之反應（第1圖之例），或從系統 外連續或脈衝式供給經前處理之載持型觸媒進行反應。又 ’亦可採用容易溶解於原料烴之雙（π 5 -環戊二烯）鐵 等有機金屬化合物作爲觸媒前驅物’連續式脈衝式饋入加 -5- (2) (2)1311544 熱區域’以觸媒前驅化合物熱分解產生之金屬粒子爲觸媒 生長碳纖維。產物捕集於加熱內部式其末端之捕集器3’ · 特定時間之反應結束後回收。 - 以氣相法製造碳纖維之方法，依觸媒或該觸媒之前驅 化合物的供給方法可大別爲以下三種。 (1)載持觸媒或其前驅化合物之氧化鋁、石墨所成 的基板、平板設置於加熱區域，與於氣相供給之烴氣體接 觸者； 參 (2 )觸媒或其前驅化合物粒子分散於液態烴等自系 統外連續式脈衝式供給於加熱區域，使之與烴於高溫接觸 者；以及 (3 )以溶解於液態烴中之金屬芳香類、羰基化合物 用作觸媒前驅化合物，將溶解有該觸媒前驅化合物之烴供 給於加熱區域，使觸媒與烴於高溫接觸者。 上述（1)之方法因有，將觸媒式其前驅物塗敷於基 板，必要時施以還原等前處理，然後製造碳纖維，降溫後 ® 取出之須獨立實施之程序，難以連續製造，生產力低。另 一方面，上述（2)及（3)之方法因可連續製造，生產力 高，一般工業上係採用（2 )或（3 )之方法。但是，若非 使用比長成產物碳纖維所需量大爲過剩之觸媒或前驅化合 物則不得足量之碳纖維，浪費大量的高價觸媒、觸媒前驅 - 物，現況係，甚至有設置去除來自過度添加之觸媒的副產 . 物之過程者。此一傾向在觸媒不以載體等載持’例如以雙 (7/ 5 -環戊二烯）鐵等觸媒前驅物以氣態或飄浮於原料 -6- (3) 1311544 氣體中之狀態供給於加熱區域產生觸媒供作使用者尤爲深 亥1J ’高活性之觸媒凝集而粗大化，長成碳纖維之能力喪失 應係原因。 以C0、甲烷、乙炔、乙烯等無機、非芳香族系烴用 於碳源’則因該等碳纖維生長速度慢，多有用於上述（！ )的方法之例’其觸媒與碳源化合物之接觸時間長達數分 鐘至數十分鐘，生產力低。 以苯 '甲苯等芳香族化合物用於碳源，則可依上述（ 2 )及（3 )之方法的連續製造，但須如上之大量過剩觸媒 或其前驅化合物，該等之有效利用率低，成本高。 經上述方法的碳纖維製造當中，一般係用一種碳化合 物作爲碳源。常有雙（-環戊二烯）鐵、噻吩之添加 ’但該等係各用作觸媒前驅物或硫之前驅物，並不期待其 單純作爲碳源。記載可用二種以上碳化合物作爲碳源之專 利文獻非常多，而具體以實施例呈示使用二種以上碳化合 物之效果者幾乎不存在。並且，有關使用二種以上碳化合 物的科學上之優點之說明的週知例全然闕如。 例如，日本專利特公平2 5 2 1 9 8 2 (專利文獻1 )揭示， 利用應係各種碳化合物之混合物的煉焦爐排氣進行碳纖維 製造。但其目的係排氣之有效利用，至於混合之際的科學 作用則毫無提及。 特開2003 - 8 1 620號公報（專利文獻2 )揭示，混合乙 炔、乙烯或丁二烯於芳香族化合物作爲碳化合物。依據該 公報，因乙炔、乙烯、丁二烯等之添加，可提高反應系之 -7 - (4) 1311544 溫度，但並無實際上混合該等碳化合物之實施例，而至於 二種碳化合物之共存的複合效果亦毫無提及。 專利文獻1特公平-25 1 982號公報 專利文獻2特開2003-81620號公報 【發明內容】 發明所欲解決之課題 本發明之目的在提供，以氣相法製造碳纖維之方法中 ，觸媒或觸媒前驅物之有效利用率巨幅提升，結果能低價 製造碳纖維的簡便且有效之方法。 用以解決課題之手段 本發明人等爲解決上述課題精心硏討結果發現，使用 (a)群：不具苯環構造之碳化合物與（b)群：芳香族化 合物之混合物於成爲碳纖維之原料的碳化合物，反應時間 即可縮短，且觸媒或觸媒前驅物之有效利用率提高，終於 完成本發明。亦即，利用本發明之方法，使用向來不可能 生長纖維之極微量觸媒，亦可於高收率製得碳纖維。又， 相較於僅用（a )群之化合物者，可於格外短之滯留時間 高生產力製得碳纖維。 導致本發明的效果之機制未必充分明瞭，但推測係因 上述（a )群化合物與觸媒作用，開始於低溫區（例如600 主1 0 0 0 c )生長纖維，生長之細纖維於達高溫區（例如 1 00 0至noo°c )之時更以（b)群化合物於纖維之粗度方 (5) (5)1311544 向（徑向）成長。因（a )群化合物之存在，於低溫區開 始纖維之生長’亦即觸媒粒子凝集、粗大化，於喪失觸媒 能力以前開始纖維之生長，故纖維或觸媒前驅物之有效利 用率巨幅提升。如此生長之細纖維因（b )群化合物之作 用纖維繼續有效成長。僅用（a )群化合物時纖維雖成長 但徑向成長緩慢，無法以高收率製造碳纖維，相對於此， (a )群化合物與（b )群化合物二者優予平衡，應即可高 效率製造碳纖維。另一方面，單獨使用（b )群化合物時 ，因於低溫區纖維生長不足，幾乎所有觸媒凝集而失去觸 媒能力，結果若非大量過剩供給觸媒或觸媒前驅物’則無 法以所欲之收率製得纖維。 亦即，本發明係關於以下之〔1〕至〔2 7〕。 〔1〕使碳化合物與觸媒及/或觸媒前驅化合物於加 熱區域接觸，於氣相製造碳纖維之方法’其特徵爲：碳化 合物係組合使用各選自下述（a)群化合物及（b)群化合 物 (a)群化合物：分子內不具苯環構造之碳化合物 (b )群化合物：芳香族化合物 之至少各一種化合物，原料中成爲觸媒之元素的原子數與 所有碳原子數之比率係 (成爲觸媒之元素的原子數）/ (所有碳原子數）= 0.000005至 0.0015 ’ (a )群化合物及（b )群化合物滿足 〔（a )群化合物所含碳原子數〕/〔 （ a )群化合物 -9 - (6)1311544 (1) Description of the Invention [Technical Field of the Invention] The present invention relates to a method for producing a high-efficiency rate of a gas phase-forming carbon fiber such as a carbon nanotube. [Prior Art] Carbon fibers (gas phase-forming carbon fibers) obtained by the gas phase growth method are relatively easy to produce carbon fibers having a high aspect ratio, and have been actively studied, and reports on manufacturing methods are also numerous. In recent years, particularly attractive carbon nanotubes (i.e., carbon fibers having a nanometer-scale fiber) can also be synthesized by the gas phase growth method. Fig. 1 is a schematic view showing an example of a reaction apparatus for continuously producing carbon fibers by a gas phase growth method. As an example of a general production method, the raw material hydrocarbon is C0, methane, acetylene, ethylene, benzene, toluene or the like. When the raw material hydrocarbon is in a normal temperature, it is supplied in a gaseous state and a carrier gas, and the liquid is vaporized and then mixed with a carrier gas, or is sprayed in a liquid state in a heating zone. The carrier gas is an inert gas such as nitrogen "reducing hydrogen" or the like. Hydrocarbons are sometimes supplied to the system under vacuum decompression. For the catalyst system, an organic metal compound such as a supported catalyst of a metal such as alumina or a bis(7?5-cyclopentadienyl) iron is supported. When a carrier-type catalyst is used, the carrier-type catalyst is previously placed in the reaction zone to be heated, and the raw material hydrocarbon is supplied to be reacted after the necessary treatment (example of Fig. 1), or continuously or pulsed from the outside of the system. The pre-treated supported catalyst reacts. Also, an organometallic compound such as bis(π 5 -cyclopentadienyl) iron which is easily dissolved in the raw material hydrocarbon can be used as a catalyst precursor. Continuous pulsed feed plus -5 - (2) (2) 1311544 heat The region 'metal particles produced by thermal decomposition of the catalyst precursor compound are catalyst-grown carbon fibers. The product is trapped in a trap 3' that heats the end of the internal type. The reaction is recovered after completion of the reaction at a specific time. - A method of producing carbon fibers by a gas phase method, and the supply method of the catalyst or the precursor of the catalyst may be as follows. (1) A substrate or a flat plate made of alumina or graphite carrying a catalyst or a precursor thereof is disposed in a heating region, and is in contact with a hydrocarbon gas supplied in a gas phase; and the catalyst (2) or its precursor compound is dispersed. The liquid hydrocarbon or the like is continuously pulsed from the system to the heating zone to be in contact with the hydrocarbon at a high temperature; and (3) the metal aromatic or carbonyl compound dissolved in the liquid hydrocarbon is used as a catalyst precursor compound. The hydrocarbon in which the catalyst precursor compound is dissolved is supplied to the heating zone to contact the catalyst with the hydrocarbon at a high temperature. In the method of the above (1), the precursor of the catalyst type is applied to the substrate, and if necessary, a pretreatment such as reduction is applied, and then the carbon fiber is produced, and the process of independently removing the product after cooling is performed, which is difficult to continuously manufacture, and productivity is difficult. low. On the other hand, the methods (2) and (3) above are continuously manufactured and have high productivity, and the industry generally adopts the method of (2) or (3). However, if the catalyst or precursor compound is not used in excess of the amount of carbon fiber required to grow into a product, the carbon fiber is not sufficient, and a large amount of high-priced catalyst, catalyst precursor, and waste are excessively disposed. By-product of the added catalyst. The process of the object. The tendency is that the catalyst is not supported by a carrier or the like, for example, a catalyst precursor such as bis(7/5-cyclopentadienyl) iron is supplied in a gaseous state or floating in the raw material -6-(3) 1311544 gas. The catalyst is generated in the heating zone for the user to be coarsened by the agitation of the high activity catalyst, and the ability to grow into carbon fiber is the cause. In the case of inorganic or non-aromatic hydrocarbons such as C0, methane, acetylene, and ethylene, which are used as carbon sources, the growth rate of these carbon fibers is slow, and there are many examples of the method used in the above (!), the catalyst and the carbon source compound. Contact time is from a few minutes to tens of minutes, and productivity is low. When an aromatic compound such as benzene'toluene is used for the carbon source, it can be continuously produced by the methods of the above (2) and (3), but a large amount of excess catalyst or its precursor compound as above is required, and the effective utilization ratio is low. ,high cost. Among the carbon fiber productions of the above methods, a carbon compound is generally used as a carbon source. There are often bis(-cyclopentadienyl) iron and thiophene additions. However, these are used as catalyst precursors or sulfur precursors, and are not expected to be purely carbon sources. There are many patent documents describing the use of two or more kinds of carbon compounds as carbon sources, and those showing the effects of using two or more kinds of carbon compounds in the examples are hardly present. Further, well-known examples of the scientific advantages of using two or more kinds of carbon compounds are completely unknown. For example, Japanese Patent Laid-Open No. 2 5 2 1 9 8 2 (Patent Document 1) discloses that carbon fiber production is carried out using coke oven exhaust gas which is a mixture of various carbon compounds. However, its purpose is to effectively use the exhaust gas, and the scientific role of mixing is not mentioned. Japanese Laid-Open Patent Publication No. 2003-86 No. 620 (Patent Document 2) discloses the mixing of acetylene, ethylene or butadiene in an aromatic compound as a carbon compound. According to this publication, the addition of acetylene, ethylene, butadiene, etc., can increase the temperature of the reaction system -7 - (4) 1311544, but there is no practical example of mixing the carbon compounds, but as for the two carbon compounds. The composite effect of coexistence is also not mentioned. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The object of the present invention is to provide a catalyst for producing carbon fibers by a vapor phase method. Or the effective utilization rate of the catalyst precursor is greatly increased, resulting in a simple and effective method for producing carbon fiber at a low price. Means for Solving the Problem The present inventors have found that the (a) group: a mixture of a carbon compound having no benzene ring structure and a mixture of (b) group: aromatic compound is used as a raw material of carbon fiber in order to solve the above problems. With the carbon compound, the reaction time can be shortened, and the effective utilization of the catalyst or catalyst precursor is improved, and the present invention has finally been completed. Namely, by using the method of the present invention, it is possible to obtain carbon fibers in a high yield by using a very small amount of catalyst which is not likely to grow fibers. Further, compared with the compound using only the group (a), the carbon fiber can be produced with an extremely short residence time and high productivity. The mechanism leading to the effect of the present invention is not necessarily fully understood, but it is presumed that due to the action of the above-mentioned (a) group compound and the catalyst, the fiber is grown in a low temperature region (for example, 600 main 1 0 0 c), and the grown fine fiber reaches a high temperature. In the region (for example, from 100 to noo °c), the (b) group compound grows (radially) in the fiber thickness (5) (5) 1311544. Due to the presence of the (a) group of compounds, the growth of fibers begins in the low temperature region, that is, the catalyst particles are agglomerated and coarsened, and the growth of the fibers is started before the loss of the catalytic ability, so the effective utilization rate of the fiber or the catalyst precursor is huge. The increase. The fine fibers thus grown continue to grow efficiently due to the fibers of the (b) group of compounds. When only the (a) group compound is used, the fiber grows slowly but the radial growth is slow, and the carbon fiber cannot be produced in a high yield. On the other hand, the (a) group compound and the (b) group compound are preferably balanced, and should be high. Efficiency in the manufacture of carbon fiber. On the other hand, when the group (b) compound is used alone, almost all of the catalyst agglomerates and loses the catalytic ability due to insufficient fiber growth in the low temperature region. As a result, if a large amount of excess catalyst or catalyst precursor is supplied, it cannot be desired. The yield was obtained by fiber. That is, the present invention relates to the following [1] to [27]. [1] A method of producing a carbon fiber in a vapor phase by contacting a carbon compound with a catalyst and/or a catalyst precursor compound in a heating zone, wherein the carbon compound is used in combination with each of the following group (a) compounds and b) Group compound (a) Group compound: a carbon compound having no benzene ring structure in the molecule (b) Group compound: at least one compound of an aromatic compound, the number of atoms of the element which becomes a catalyst in the raw material, and the number of all carbon atoms Ratio (the number of atoms that become the element of the catalyst) / (all carbon atoms) = 0.000005 to 0.0015 ' (a) Group compound and (b) group compound satisfy [(a) group of carbon atoms contained in the group] / [ (a) Group of compounds - 9 - (6)
I 1311544 所含碳原子數+ ( b)群化合物所含碳原子數〕=〇·001至 0.9 之條件，於6 0 0 t：以上之溫度範圍的滯留時間係3 0秒以下 〇 〔2〕如上述〔1〕的以氣相法製造碳纖維之方法’其 中原料中成爲觸媒之元素的原子數與所有碳原子數之比率 係 (成爲觸媒之元素的原子數）/(所有碳原子數）= 0.00001 至 0.001 〇 〔3〕如上述〔1〕的以氣相法製造碳纖維之方法’其 中原料中成爲觸媒之元素的原子數與（b)群化合物所含 碳原子數之比率係 (成爲觸媒之元素的原子數）/ ( (b)群化合物所含 之碳原子數）=〇·〇〇〇〇〇5至0·0015。 〔4〕如上述〔3〕的以氣相法製造碳纖維之方法’其 中原料中成爲觸媒的元素之原子數與（b)群化合物所含 碳原子數之比率係’ (成爲觸媒之元素的原子數）/( (b)群化合物所含 之碳原子數）=0.0000 1至0.001。 〔5〕如上述〔1〕的以氣相法製造碳纖維之方法’其 中原料中成爲觸媒之元素的原子數與（a)群化合物所含 之碳原子數的比率係 (成爲觸媒之元素的原子數）/ (a)群化合物所含之 碳原子數=〇·0000 1至ο.1· -10- (7) (7)1311544 〔6〕如上述〔5〕的以氣相法製造碳纖維之方法’其 中原料中成爲觸媒之元素的原子數與（a )群化合物所含 ‘ 碳原子數之比率係 - (成爲觸媒之元素的原子數）/ ( ( a )群化合物所含 之碳原子數）= 0.000 1至ο.1。 〔7〕如上述〔1〕的以氣相法製造碳纖維之方法’其 中原料中成爲觸媒之元素的原子數與（b)群化合物所含 碳原子數之比率係 鲁 (成爲觸媒之元素的原子數）/( (b)群化合物所含 之碳原子數）=0.00〇〇〇5至0_0015，並且原料中成爲觸媒 之元素的原子數與（a)群化合物之碳原子數的比率係 (成爲觸媒之元素的原子數）/ ( ( a )群化合物所含 碳原子數）= 0.0000 1至0 〔8〕如上述〔7〕的以氣相法製造碳纖維之方法’其 中原料中成爲觸媒的元素之原子數與（b)群化合物所含 碳原子數之比率係 ^ (成爲觸媒之元素的原子數）/( (b)群化合物所含 碳原子數）= 0.00001至0.001 ’並且原料中成爲觸媒之兀 素的原子數與（a )群化合物所含碳原子數之比率係 (成爲觸媒之元素的原子數）/ ( (a)群化合物所 含碳原子數）=0.000 1至0.1 ° . 〔9〕如上述〔1〕的以氣相法製造碳纖維之方法’其 中使（a )群化合物及（b )群化合物以滿足 ((a )群化合物所含之碳原子數）/ ( ( a )群化合 -11 - (8) 1311544 物所含碳原子數+ (b)群化合物所含之碳原子數）= 0.003至 〇·5 之條件的比率供給於反應反應器之加熱區域。 〔10〕如上述〔1〕的以氣相法製造碳纖維之方法， 其中使（a )群化合物及（b )群化合物以滿足 ((a )群化合物所含碳原子數）/ ( ( a )群化合物 所含碳原子數+ (b)群化合物所含碳原子數）=〇. 〇〇5至 0.2 之條件的比率供給於反應器的加熱區域。 〔1 1〕如上述〔1〕至〔1 〇〕中任一的以氣相法製造 碳纖維之方法，其中（a)群化合物係選自一氧化碳、一 氧化碳、飽和脂肪族化合物、飽和脂環式化合物所成群之 至少一種化合物。 〔12〕如上述〔1〕至〔1 0〕中任一的以氣相法製造 碳纖維之方法，其中（a)群化合物係選自一氧化碳、二 氧化碳、飽和脂族烴、飽和脂族醇、飽和脂族胺、飽和脂 族硫醇、飽和脂族酯、飽和脂族醚、飽和脂族醛、飽和脂 族羧酸、飽和脂環烴、飽和脂環醇、飽和脂環胺、飽和脂 環硫醇、飽和脂環酯、飽和脂環醚、飽和脂環醛 '飽和脂 環羧酸所成群之至少一種化合物。 〔1 3〕如〔1〕至〔〗2〕中任一的以氣相法製造碳纖 維之方法，其中（a )群化合物之沸點（1大氣壓）不及80 t。 〔Μ〕如〔1〕至〔I 2〕中任一的以氣相法製造碳纖 -12- (9) 1311544 維之方法’其中（a )群化合物係選自一氧化碳、二氧化 碳、甲醇、乙醇、甲烷、乙烷、丙烷及丁烷所成群之至少 一種化合物。 〔1 5〕如〔1〕至〔1 4〕中任一的以氣相法製造碳纖 維之方法’其中（b)群化合物係選自芳族烴之至少一種 化合物。 〔1 6〕如上述〔1〕至〔1 5〕中任一的以氣相法製造 碳纖維之方法，其中（b)群化合物係選自苯、甲苯、二 甲苯、乙苯、苯乙烯、 所成群之至少一種化合物。 〔1 7〕如上述〔1〕至〔1 0〕中任一的以氣相法製造 碳纖維之方法，其中（a )群化合物係選自一氧化碳、二 氧化碳、甲醇、乙醇及甲烷所成群之至少一種化合物，（ b )群化合物係選自苯、甲苯及二甲苯所成群之至少一種 化合物。 〔1 8〕如上述〔1〕至〔1 7〕中任一的以氣相法製造 碳纖維之方法，其中原料通過6〇〇 °C以上，不及1 0 00 °C之 低溫度區及1 〇 〇 〇 °c以上之高溫度區。 〔1 9〕如上述〔1 8〕之以氣相法製造碳纖維之方法， 其中使包含碳化合物與觸媒及/或觸媒前驅化合物之原料 組成物於低溫度區之滯留時間爲0.5秒以上。 〔2 0〕如上述〔1 8〕或〔1 9〕的以氣相法製造碳纖維 之方法，其中（a )群化合物於導入低溫區後’將（b )群 化合物導入高溫區。 〔2 1〕如上述〔1〕至〔2 0〕中任一的以氣相法製造 -13- (10) (10)1311544 碳纖維之方法，其中於氣體狀態供給（a )群化合物、（b )群化合物及觸媒前驅物於加熱區域。 〔2 2〕如上述〔1〕至〔2 1〕中任一的以氣相法製造 碳纖維之方法，其中觸媒前驅化合物含選自18族型元素週 期表中之第3' 5、6、8、9、1〇族之至少一種金屬。 〔23〕如上述〔1〕至〔22〕中任一的以氣相法製造 碳纖維之方法，其中反應後之氣體的全部或部份經循環再 利用。 〔24〕如上述〔1〕至〔2 3〕中任一的以氣相法製造 碳纖維之方法，其中製造平均纖維徑奈米以上之碳纖維 〇 〔25〕如上述〔1〕至〔24〕中任一的製造方法製造 之氣相成之碳纖維。 〔26〕如上述〔25〕之氣相法碳纖維’其中殘留觸媒 含量在5 000 ppm (重量）以下。 〔27〕如上述〔25〕之氣相法碳纖維，其中殘留觸媒 含量係500 ppm (重量）以下° 發明之效果 依據本發明，以（a )群化合物及（b )群化合物二者 用作碳源，可於極少觸媒量以高生產力製得碳纖維。 【實施方式】 以下，必要時參照圖式更具體說明本發明。 -14- (11) (11)1311544 (碳化合物） 本發明的碳纖維之製造方法中，成爲碳纖維原料之碳 化合物（含碳原子之化合物）係選自以下（a )群之至少 一種化合物與選自（b )群之至少一種化合物的混合物。 (a)群：分子內不具苯環構造之碳化合物 (b )群：芳香族化合物 (a )群化合物之第一條件爲，係分子中不具苯環之 化合物。在此所謂苯環包含苯縮合萘骨架，葸骨架等縮合 環。苯環之一部份碳以氧、氮、硫等取代之呋喃、吡啶、 噻吩等所謂雜環之亦解釋作苯環或縮合環者不得包含作（ a )群化合物之單元。 碳纖維可謂係，碳化合物分解生成之碳物種於加熱區 域溶解或固溶於觸媒中，其經析出而生成。（a )群化合 物之要求功能係，容易變爲易於氫化分解溶解於觸媒之碳 物種。因此，難以直接溶解於觸媒的分子內有苯骨架之化 合物即不合適。 因此，（a )群化合物有一氧化碳、二氧化碳、脂肪 族化合物及脂環式化合物等。其中脂肪族化合物及脂環式 化合物係，脂族烴、脂環烴及其衍生物而分子內不具苯環 或縮合環之化合物。脂族烴及脂環烴、飽和者較不飽和者 爲佳。飽和者較佳之理由應係容易變爲易於氫化分解溶解 於觸媒之碳物種。又，（a )群化合物除碳及氫以外亦可 含氮、磷'氧、硫、氟、氯、溴、碘等元素。 -15- (12) (12)1311544 又，爲充分發揮本發明之效果，（a )群化合物宜於 低溫區與觸媒或觸媒前驅物均勻混合。因而（a )群之化 合物爲於低溫區與氣態或飄浮於原料氣體中之狀態下的觸 媒或觸媒前驅物均勻混合須經氣化1故以易於氣化者爲佳 ’更如後敘，以充分混合（a )群及（b )群之化合物供給 於加熱區域爲佳，爲其實現’以（a )群及（b )群化合物 一併於氣化狀態下混合爲最佳。因此’（a )群化合物係 以1大氣壓下之沸點不及180 °C者爲佳’不及80 °C ’甚至於 不及60°C更佳，最佳者爲不及20C。 基於以上，（a)群化合物之例有，一氧化碳、二氧 化碳等無機氣體；碳原子數1至8之烷類；碳原子數3至8之 環烴類等。 較佳（a )群化合物之例有一氧化碳、二氧化碳等無 機氣體；甲苯'乙烷、丙烷、丁烷、戊烷'己烷、庚烷、 辛烷等烷類；環丙烷、環戊烷 '烷己烷等環烷烴類等° 使這些烴含氧、氮、硫、磷、鹵素等之衍生物’例如 甲醇、乙醇、丙醇、丁醇等含氧化合物，甲硫醇、甲乙硫 醚、二甲基硫酮等含硫脂族化合物，氯仿、四氯化碳、氯 乙烷等鹵化烴等亦可使用。 更佳之（a)群化合物有一氧化碳、二氧化碳、甲醇 、乙醇、甲烷、乙烷、丙烷及丁烷，最佳之（a )群化合 物有一氧化碳、二氧化碳、甲醇、乙醇及甲烷。 (b )群芳香族化合物係指芳烴及其衍生物，具有苯 環之所有化合物。以芳烴爲佳，但含碳及氫以外之氮、硫 -16- (13) 1311544 、氧、硫、氟、氯、溴、碘等元素亦無妨。（b )群化合 物之功能係，沈積於生成之碳纖維上，碳化而使碳纖維於 徑向成長’以分子內有苯環之化合物爲合適。 較佳（b)群化合物之例有苯、甲苯、二甲苯、苯乙 烯、乙苯、及等單環芳族烴；茚、萘、蒽、菲等具縮合環 之多環化合物等。 這些（b )群芳香族化合物亦可使用含氧、氮、硫、 磷、鹵素等之衍生物，例如苯硫醇、二苯硫醚等含硫芳族 化合物等。高沸點之芳香族化合物亦可使用，但爲與（a )群化合物優予混合以易於氣化者爲有利，沸點較低之化 合物爲佳。 因此，特佳之（b)群化合物有苯、甲苯、二甲苯、 乙苯、苯乙烯、5等。 本發明係以（a )群化合物與（b )群化合物之倂用爲 必要條件。以甲苯、乙苯等具烷基之芳香族化合物用作（ b)群化合物時，於加熱區域或其前之升溫途中分解’附 於苯環之烷基等預測亦具如同（a )群化合物之效果。但 是，單以乙苯供給時，如嗣後比較例2所示，無法實現本 發明之效果。易言之，於分解等之結果能提供（a )群及 (b )群之化合物的化合物之供給並不滿足本發明之要件 。於具有加熱到6 0 0至1 3 5 0 °C左右之溫度的部份之反應器 ，以（a )群化合物及（b )群化合物供給方係本發明本質 上之要件。 (a )群化合物與（b )群化合物之使用比率’係以（ -17 - (14) (14)1311544 (a )群化合物所含之碳原子數）/ ( ( a )群化合物所含 之碳原子數+ (b)群化合物所含之碳原子數）=〇.〇〇1至 0.9爲佳。更佳者爲（（3)群化合物所含碳原子數）/ ( (a )群化合物所含碳原子數+( b )群化合物所含碳原子 數）= 0.003至0.5。更佳者爲（（a)群化合物所含之碳原 子數）/( (a)群化合物所含之碳原子數+ (b)群化合 物所含之碳原子數）=0.005至0.2。（ a )群化合物少量添 加即具效果’過量添加則容易產生非纖維狀之固體成分’ 纖維比率下降。另一方面，以一氧化碳等大量用作（a) 群化合物，生產力亦不提升，收率極低。因此’上述範圍 爲較佳。 例如，（a)群化合物乙烯以〇·4毫莫耳/分鐘’ （b )群化合物苯以1 _ 2 〇毫莫耳/分鐘之速率連續供給於反應 器加熱區域時，（a )群化合物所含碳原子數之供給速率 爲〇.8毫莫耳/分鐘（乙烯之碳原子數係2’故〇.4x2=〇.8 ),(b)群化合物所含碳原子數之供給速率爲7 ·2〇毫旲 耳/分鐘（苯之碳原子數係ό,故1.20x7=7.20) ’ ( (a )群化合物所含碳原子數）/(( a )群化合物所含碳原 子數+ (b)群化合物所含碳原子數）= (〇.8 (觸媒） 本發明中，觸媒須係促進碳纖維生長之物質’無特殊 限刹。該觸媒有例如，IU P A C於1 9 9 0年提倡之1 8族型元素 -18- (15) 1311544 週期表中選自第3至丨2族之至少一種金屬。以選自第3、5 、6、8、9、1 〇族所成群之至少一種金屬爲更佳，鐵、鎳 、鈷、釕、铑 '鈀、鉑及稀土元素者爲特佳。 (觸媒前驅化合物） 觸媒前驅化合物係指經加熱而熱解，有時更經還原供 給上述觸媒之化合物。例如’觸媒前驅化合物雙（々5 一 環戊二烯）鐵經加熱而熱解，生成觸媒鐵微粒。因此，供 給如上之金屬的化合物即適用作觸媒前驅化合物。更具體 的觸媒前驅化合物之例，以含選自第3至1 2族所成群之至 少一種元素的金屬化合物，尤以含選自第3、5、6、8、9 、1 〇族所成群之至少—種元素的化合物爲佳’含鐵 '鎳、 鈷、釕、鍺、鈀、鉑及稀土元素之化合物爲最佳。 並可於這些主成分加入含選自第1至17族所成群之至 少一種元素的金屬化合物作爲觸媒之改質成分（所謂助觸 媒），調整主成分金屬觸媒性能。 (載體） 上述觸媒及/或觸媒前驅物，必要時亦可載持於載體 使用。該等載體以於加熱區域安定之化合物爲佳，這些化 合物之例有，氧化鋁、氧化矽、沸石、氧化鎂、氧化鈦、 氧化锆、石墨、活性碳、碳纖維等。 (觸媒等之使用量） -19 - (16) (16)1311544 觸媒或觸媒前驅化合物之使用量係以’成爲觸媒之713 素（例如Fe )的原子數與原料碳化合物中的碳莫耳數（亦 即，碳化合物等原料中所有的碳原子數）之比率爲 0.000005 至 0.0015 爲佳，0.00001 至 o.ool 更佳 ’ 〇.0001 至 0.0005又更佳，0.0002至0.0004爲最適。少於0·000005則 觸媒不足，纖維數減少，纖維徑增大，故不佳。該比大於 0 · 0 0 1 5則不只不經擠，且會有不具觸媒功能之粗大觸媒粒 子混入纖維故不佳。而上述原料中所有碳原子重量比率之 計算中，所有碳原子莫耳數之計算係，不僅碳化合物’亦 包含來自觸媒前驅化合物、助觸媒、載體等添加成分 '溶 劑之碳原子。 成爲觸媒之元素的原子數與（a)群化合物所含碳原 子數之比率係以（成爲觸媒之元素的原子數）/( (a) 群化合物所含之碳原子數）= 0.00001至0.1之範圍爲佳。 更佳者爲（成爲觸媒之元素的原子數）/( (a)群化合 物所含碳原子數）= 0.0001至0.1。尤佳者爲（成爲觸媒 之元素的原子數）/( (a)群化合物所含碳原子數）= 0.001至0.01。相對於觸媒（a)群化合物過多則低溫區觸 媒不起作用之（a )群化合物變多。觸媒不起作用而直接 抵達高溫之（a )群化合物幾不參與纖維之生成' 成長， 其量大則一部份成爲非纖維狀之例如球狀的固體產物。相 對於觸媒（a )群化合物過少則無法充分抑制觸媒之凝集 ，觸媒的有效利用率變差，纖維產量變少。有時，在高溫 區不利用於纖維成長之（b )群化合物變成非纖維狀之例 -20- (17) (17)1311544 如球狀固體產物混入。 成爲觸媒之元素的原子數與（b)群化合物所含碳原 子數之比率係以（成爲觸媒之元素的原子數）/(( b ) 群化合物所含之碳原子數）=〇.000005至0,0015之範圍爲 佳。更佳者爲（成爲觸媒之元素的原子數）/( (b)群 化合物所含碳原子數）=0.00001至0·001’尤佳者爲（成 爲觸媒之元素的原子數）/( (a)群化合物所含碳原子 數）=0_00005至0.0〇1。相對於觸媒（15)群化合物過多 則於高溫區（b )群化合物快速分解而碳化’纖維成長以 外會生成非纖維狀之例如球狀的固體產物。相對於觸媒（ b )群化合物過少則生成之碳纖維成長不足’收率無法提 升，生產力低。 原料中成爲觸媒之元素的原子數與（b)群化合物所 含碳原子數之比率係以（成爲觸媒之元素的原子數）/ ( (b)群化合物所含碳原子數）=〇.000005至0·0015’且 原料中成爲觸媒之元素的原子數與（a)群化合物所含碳 原子數之比率，（成爲觸媒之元素的原子數）/ ( (a) 群化合物所含碳原子數）= 〇·〇0001至ο·1爲佳。又，原料 中成爲觸媒之元素的原子數與（b )群化合物所含碳原子 數之比率’以（成爲觸媒之元素的原子數）/( (b)群 化合物所含碳原子數）=〇.〇〇〇01至0.001’且原料中成爲 觸媒之元素的原子數與（a)群化合物所含碳原子數之比 率，（成爲觸媒之元素的原子數）/ ( (a)群化合物所 含之碳原子數）= 0.0001至〇.丨爲更佳。 -21 - (18) (18)1311544 (原料之供給方法） 原料之供給方法無特殊限制。可將（a )群化合物、 (b )群化合物，觸媒及/或觸媒前驅化合物全予氣化以 氣態供給，亦可其一部份或全部以液態供給。這些化合物 之內，可先供給（a )群化合物與觸媒及/或觸媒前驅化 合物，反應系之途中起供給（b )群化合物，但以同時供 給爲佳。但是，一較佳樣態可係，先供給（a )群化合物 與觸媒及/或觸媒前驅化合物於後敘低溫區域，供給（b )群化合物於後敘高溫區域。（a )群化合物、（b )群化 合物更於下示之載氣等的混合不充分時，反應系內會有（ a)群化合物濃度低之部份、（b )群化合物濃度低之部份 ，（a )群化合物之效果減弱。因此，導入加熱區域前使 這些原料氣化以氣態物充分混合後供給於加熱區域乃屬特 佳0 (載氣） 本發明之以氣相法製造碳纖維時，除這些組成物以外 宜使用載氣。載氣可用氫、氮、氨、氬、氪、或這些的混 合氣體。但是，空氣等含氧分子（亦即分子狀態之氧： )之氣體則不合適。用於本發明之觸媒前驅化合物有時係 氧化狀態，此時載氣係以使用含氫之氣體爲佳。因此’較 佳載氣係含氫1體積％以上，30體積％以上更佳，_85體積 %以上氣體爲最佳，例如，1 〇〇體積％之氫或以氮稀釋之 -22- (19) (19)1311544 氫的氣體。 (硫化合物） 本發明之以氣相法製造碳纖維時亦可倂用有控制碳纖 維徑之效果的硫化合物。可將硫、噻吩、硫化氫等化合物 以氣態或溶解於溶劑供給。當然亦可使用該（a )群化合 物、該（b )群化合物’該觸媒前驅化合物中含硫之物質 。所供給之硫的總莫耳數宜係成爲觸媒之莫耳數的1 〇〇〇倍 以下’ 1 〇〇倍以下較佳，1 〇倍以下更佳。供給之硫的量過 大則不經濟，或亦成爲妨礙碳纖維生長之原因故不佳。 (碳纖維之合成） 以氣相法之碳纖維合成，係將以上說明之原料及必要 時之載氣供給於加熱區域，於加熱下接觸而達成。反應器 (加熱爐）若係可得特定之滞留時間、加熱溫度者即無特 殊限制，而直立或橫臥式管狀爐則於原料供給、滞留時間 控制上較佳》 加熱區域之溫度隨所用碳化物之種類而大有不同。一 般宜係5 00°c以上1 5 00°C以下’ 800 °C以上1 3 5 0 °c以下更佳 。溫度過低則不長成碳纖維’如果過高則不長成碳纖維， 或僅得粗纖維。 本發明係倂用（a )群化合物、（b )群化合物作爲碳 原。（a )群化合物、（b )群化合物其有助於碳纖維之生 成、成長之溫度不同。因此無特殊限制，加熱區域之溫度 -23- (20) (20)1311544 亦非一定，較佳者爲能於（a )群化合物起作用之低溫區 之後，有（b )群化合物起作用之高溫區。二溫度區域之 — 溫度分布有，具低溫區及高溫區二加熱區域’或使低溫區 - 至高溫區有斜率’溫度慢慢變高等等。 低溫區係（a )群化合物有效率地因觸媒起作用之溫 度區，以6001至1〇〇〇 °C爲佳’ 700 °c至1000 °C更佳。該溫 度過低則（a )群化合物不因觸媒起作用’或即使作用反 應速率亦慢，無法充分生成碳纖維。溫度過高則（a )群 · 化合物因觸媒起作用前大量觸媒凝集’觸媒之有效利用率 降低，纖維成長以外的狀態之產物’例如球狀產物大量產 生。 高溫區係（b )群化合物有效率地作用於碳纖維，使 碳纖維成長之溫度區，以1〇〇〇 °c至15〇〇 °c爲佳，1〇〇〇 °c至 1 3 5 ot更佳。該溫度過低則（b )群化合物不分解，無助 於纖維成長。溫度過高則（b )群化合物急劇分解，纖維 成長以外之狀態的產物，例如球狀產物大量產出。 低溫區之滞留時間以0.1秒以上爲佳，0.5秒以上更佳 。更佳者爲1 _ 〇秒以上。該時間過短則會有碳纖維之無法 充分生成。高溫區之滯留時間以在0.000 1秒至60秒以內即 可，0_001至30秒更佳，〇.〇1至15秒最佳。滯留時間過短 則碳纖維不成長，過長則有時僅得粗纖維。可於短滯留時 . 間以高收率、高生產力製得碳纖維之本發明，滯留時間太 _ 長即不佳。 滯留時間係以加熱區域之長度及載氣流量調整。隨所 -24 - (21) 1311544 用之反應裝置、碳化合物的種類而大有不同。滯留時間過 短則碳纖維不成長，過長則有時僅得粗纖維。 本發明中低溫區及高溫區之合計滯留時間，即6 〇 〇 以上溫度範圍之滯留時間可係0 . 1秒至3 0秒，以0 · 5秒至3 0 秒爲佳，1.0秒至1 6秒更佳。 6〇〇°C以上溫度區之滯留時間係反應氣體經加熱，自 超出60 0 °C之低溫區溫度升溫至高溫區溫度，然後冷卻下 降至60 0°C之時間。低溫區之滯留時間係升溫時自超出600 °C至超出1 0 0 0 °c之時間。高溫區之滞留時間係超出1 〇 〇 〇 I 後降溫至1 0 0 0 °c以下爲止之時間。 低溫區之反應及高溫區之反應亦可個別進行。此時， 低溫區之滯留時間係，超出發生低溫區之反應的600 °c， 保持於1 000 °C以下並下降至600 °c之時間，及其後發生高 溫區反應時升溫時超出600 °c起至超出100CTC之時間的和 。低溫區及高溫區之合計滯留時間係，發生低溫區反應時 及以發生高溫區反應時二者，反應氣體在60(TC以上之時 間的和。 碳纖維生成反應通常係在一根反應管內進行。此時’ 流量若一定，滯留時間可由流速之改變（反應管徑之改變 )，或加熱帶之長度的改變加以調整。 高溫區之時間極長，（b )群化合物幾乎全部分解時 ，反應後之氣體中碳化合物主要成分係甲烷 '乙烯。反應 氣體中含有含氧化合物時，於其加一氧化碳、二氧化碳。 (b )群化合物之分解不完全時分解產生之氣體主要成分 -25 - (22) (22)1311544 與上述（1 )同。以該反應後之氣體的全部或部份直接’ 或經（a )群化合物及/或（b )群化合物之追加’再次供 給於過熱之區域，可循環、再使用。將反應後之氣體循環 、再使用時’原料中（a )群化合物、（b )群化合物等之 量係，含於循環、再使用之氣體的量與追加量之合計。 反應裝置之一例如第2圖。此時，具備加熱器2 — 1 ’ 上部有導入載氣、（a)群化合物，（b)群化合物以及觸 媒或觸媒前驅化合物之管線。下部有’捕集生成之碳纖維 的容器。使用此種裝置，以加熱器2 — 1加熱至高溫區之特 定溫度，導入反應爐內之反應氣體自室溫抵達高溫區的特 定溫度之間通過低溫區之滯留時間1以反應氣體流量之調 整等使其滿足上述條件即可。 又本發明中宜有低溫區、高溫區之二溫度區域的區別 ，故亦可使用如第3圖之具備能獨立控制這些溫度區域之 加熱器2— 1、加熱器2— 2的反應裝置。此時以加熱器2一1 升溫至低溫區之特定溫度，以加熱器2 - 2升溫至高溫域之 特定溫度，使含載氣、（a )群化合物、（b )群化合物及 觸媒或觸媒前驅化合物等之混合氣體流過反應裝置內，可 得碳纖維。第3圖中，加熱器2 - 1及加熱器2 — 2係連續設 置，但亦可個別設置加熱器，—旦通過加熱器2 - 1後’將 氣體溫度降至低於低溫區之溫度後’以加熱器2 - 2加熱至 高溫區。 本發明之特徵係，供給之碳源有效率地以碳纖維回收 。其機制基本上係（a )群化合物與觸媒接觸生成之纖維 -26 - (23) (23)1311544 ’主要以（b )群化合物爲碳源，於徑向有效加粗。因此 ，不適於所謂單壁、雙壁等外徑極小的碳纖維之製造 > 而 係非常適合於較粗纖維之製造。亦即，最適作纖維平均外 徑10奈米以上，50奈米以上較佳，尤以80奈米以上，最佳 者1 0 0奈米以上之碳纖維的製造方法。在此所謂碳纖維之 外徑可由例如，由SEM照相測定1 00根左右纖維之外徑而 求出。或亦可由BET比表面積假設爲圓柱體而算出。 利用本發明，觸媒或觸媒前驅物之利用效率可顯著提 升。亦即，以小量觸媒即可高效率製得碳纖維》以通常方 法製造之碳纖維殘留有5 0000重量ppm左右之觸媒（鐵等 )。爲提升所製造的碳纖維之物性，可施以煅燒（1 500°C 左右）、惰性氣體下之石墨化處理（2 0 0 0至3 0 0 0°C )。此 際，觸媒鐵等一部份氣化 '蒸發，故石墨化處理後之碳纖 維中觸媒殘留量降低。另一方面’利用本發明之製造方法 ，可使碳纖維中之觸媒含量在不施以煅燒 '石墨化等處理 之狀態下亦係極低。觸媒含量在不施以煅燒、石墨化等處 理之狀態下，可係5⑽0 P p m以下，較佳條件下可得5 0 0 p p m以下之碳纖維。取決於用途，石墨化處理可以不必。 又，本發明之方法中可見’隨（a)群化合物所含碳 原子數與（b )群化合物所含碳原子數比率之變化，所得 纖維之平均外徑有起變化之傾向。易言之’ （a )群化合 物所含碳原子數之比率增大則纖維徑變小’反之比率減小 則纖維徑變大。此呈示’不藉反應裝置、條件之細小變更 ，僅作原料碳化合物組成之變動即可控制所得碳纖維之平 -27- (24) 1311544 均外徑。例如纖維外徑80至150奈米範圍之碳纖維可非常 簡單地製得。 ^ 實施例 以下舉實施例更詳細說明本發明，但本發明不限於此 〇 以下實施例、比較例中所用之試藥等如下。 〔試藥類〕 1 · ( a )群化合物 一氧化碳：日本氧氣（股） 二氧化碳：相模乙炔（股） 甲烷：高千穗商事（股） 乙烯：日本氧氣（股） 甲醇：和光純藥工業（股） 乙醇：和光純藥工業（股） _ 2. ( b )群化合物 苯：和光純藥工業（股） 甲苯：和光純藥工業（股） 對二甲苯：和光純藥工業（股） 乙苯：和光純藥工業（股） 3 .觸媒前驅化合物 -28- (25) (25)1311544 雙（77 5 -環戊二烯）鐵：日本ΖΕΟΝ (股） 4.其它成分 噻吩：和光純藥工業（股） 〔碳纖維之合成〕 <實施例1 > a :乙烯、b :苯 利用第2圖之具備石英製反應管1 (內徑3 1毫米，外徑 3 6毫米，加熱區域長度約4 0 0毫米）之直立型爐，N2氣流 中使加熱區域升溫至1 2 5 0 °C，然後，切斷N2之供給，改以 1標準升/分鐘流通載氣H2於反應管內。溫度穩定後，乙 烯（（a )群化合物）於氣態與H2混合。苯（（b )群化合 物）、雙（^5 —環戊二烯）鐵及噻吩溶解混合，其液用 小型泵使各成分以表1之導入量於10分鐘導入加熱至200 °C 之氣化器4氣化、與H2&乙烯之混合氣體合倂。如此，所 有化合物以氣態供給於反應管內。 反應結果，於反應管底部至捕集器之間有帶灰色的蜘 蛛巢狀沈積物之生成》降溫後回收該沈積物，回收量除以 當初所用碳化合物所含之碳量，求出碳回收率。並以掃猫 式電子顯微鏡觀察蜘蛛巢狀之生成物。結果列於表1。生 成物係平均外徑1 5 0奈米之纖維狀物，碳回收率係3 5 % ° 又，此時600 °C以上不及1 000 °C的低溫區之滯留時間係約 0_6秒，60 0 °C溫度區的滯留時間約3.7秒。 -29- (26) (26)13 Π 544 〈貫施例2 > a :甲烷、b :苯 除取代乙烯改用甲烷以外，依實施例1之方法進行反 應。結果列於表1。產物係平均外徑1 5 0奈米之纖維狀物’ 碳回收率35%。 〈實施例3> a: —氧化碳、b:苯 除取代乙烯改用一氧化碳以外’依實施例1之方法進 行反應。結果列於表1。產物係平均外徑1 5 0奈米之纖維狀 物’碳回收率35%。 <實施例4> a:二氧化碳、b:苯 除取代乙烯改用二氧化碳以外，依實施例1之方法進 行反應。結果列於表1。產物係平均外徑1 5 0奈米之纖維狀 物’碳回收率3 5 %。 <實施例5> a:甲醇、b;苯 不用乙烯，以甲醇一倂溶解混合苯、雙（^ 3 —環戊 二烯）鐵及噻吩導入以外，如同實施例1反應。結果列於 表1。產物係平均外徑1 5 0奈米之纖維狀物’碳回收率3 8 % <實施例6 > a :乙醇、b ;苯 不用乙烯’以乙醇一倂溶解混合苯、雙（々3 —環戊 二烯）鐵及噻吩導入以外，如同實施例1反應。結果列於 -30 - (27) (27)1311544 表1。產物係平均外徑1 5 0奈米之纖維狀物’碳回收率3 1 % <實施例7 > a :甲醇、b ;苯 取代苯改用甲苯以外依實施例1之方法進行反應。結 果列於表1。產物係平均外徑150奈米之纖維狀物’碳回收 率 37%。 <實施例8 > a :乙烯、b ;苯 乙烯導入量減半至如表1的値以外依實施例1之方法進 行反應。結果列於表1。產物係平均外徑1 5 0奈米之纖維狀 物，碳回收率3 6 %。 <實施例9> a:甲烷、b;甲苯 取代乙烯改用甲烷，並取代苯改用甲苯以外依實施例 | 1之方法進行反應。結果列於表1。產物係平均外徑1 5 0奈 米之纖維狀物，碳回收率3 7 %。 <實施例1 0 > a :甲烷、b ;對二甲苯 取代乙烯改用甲烷’並取代苯改用對二甲苯以外依實 施例1之方法進行反應。結果列於表1。產物係平均外徑 150奈米之纖維狀物，碳回收率35%。 <實施例1 1 > a :—氧化碳、b :苯 -31 - (28) (28)1311544 改變一氧化碳之用量以外依實施例3之方法進行反應 。結果列於表1。產物係平均外徑1 5 0奈米之纖維狀物’ 回收率2 0 %。 <實施例1 2 > a : 一氧化碳、b :苯 改變一氧化碳之用量以外依實施例3之方法進行反應 。結果列於表1。產物係平均外徑1 5 0奈米之纖維狀物’碳 回收率2 7 %。 <實施例1 3 > a :甲烷、b :苯 改變甲烷及苯之用量以外依實施例2之方法進行反應 。結果列於表1。產物係平均外徑1 0 0奈米之纖維狀物’碳 回收率24%。 <實施例1 4 > a :甲烷、b :苯 改變甲烷及苯之用量以外依實施例2之方法進行反應 。結果列於表1。產物係平均外徑8 0奈米之纖維狀物’碳 回收率1 8 %。 <實施例1 5 > a :甲烷、b :苯 改變甲烷、雙（7/5 -環戊二烯）鐵、噻吩之用裏以 外依實施例2之方法進行反應。結果列於表1。產物係平均 外徑1 00奈米之纖維狀物，碳回收率3 5 %。 -32- (29) 1311544 〈實施例1 6 > a :甲烷、b :苯 改變甲院、苯、雙（^―環戊二烯）鐵、€ 量以外依實施例2之方法進行反應。結果列於表1。 平均外徑1 5 0奈米之纖維狀物，碳回收率6 〇 %。 <比較例1、2 > 不用乙嫌，只用苯或乙苯作爲（b)群化合物 如同實施例1反應。回收之固體物幾乎全係球狀碳 果列於表1。 <比較例3 > 於如第4圖之具備石英製反應管1 (內徑31毫米 36毫米，加熱區域長度約4〇〇毫米）之直立式爐’ 化器4、N2經旁通管5流過’一面將加熱區域升溫至 ，然後切斷N2之供給’經旁通管5以1標準升/分鐘 管內流過載氣H2。溫度穩定後，以表1之量的乙烯 與載氣混合。然後於已預先饋入雙（7? 5 -環戊二 加熱至l4〇°C之氣化器4’由旁通管5導入之載氣與 合氣體分出一部份’以3 3毫升/分鐘之流量流過。 1之量的噻吩導入氣化器（原料液成分）雙（77 5 一 烧）鐵及噻吩於氣態倂合於載氣與乙稀之混合氣體 與旁通管5合流’所有的化合物以氣態供給於反應管 氣化器4之溫度及應注入之載氣與乙烯的混合 量’係先查出能導入表1之量的雙（〇 5 —環戊二烧 吩之用 產物係 以外， 粒。結 ，外徑 不經氣 1 2 5 0 °C 於反應 於氣態 烯）鐵 乙烯混 更以表 環戊二 ，混合 ;內。 氣體流 )鐵之 -33- (30) (30)1311544 條件使用該條件。 而本比較例中因不使用將固態之雙（77 5 -環戊二烯 - )鐵溶解，以供給於氣化器4之液體成分（例如苯），先 . 雙（7? 5 -環戊二烯）鐵饋入氣化器，使之升華。噻吩係 液體，但用量不足以溶解雙（7/5 —環戊二烯）鐵。 回收之固體成分幾乎都是球狀物，有一部份係纖維狀 物。I 1311544 contains the number of carbon atoms + (b) the number of carbon atoms in the group of compounds] = 〇 · 001 to 0.9, the residence time in the temperature range of 600 ton: above is less than 30 seconds 〇 [2] The method for producing carbon fibers by a gas phase method according to the above [1], wherein the ratio of the number of atoms of the element which becomes a catalyst in the raw material to the number of all carbon atoms (the number of atoms which become the element of the catalyst) / (all carbon atoms) ) = 0.00001 to 0.001 〇 [3] The method for producing carbon fibers by a gas phase method according to the above [1], wherein the ratio of the number of atoms which become a catalyst element in the raw material to the number of carbon atoms contained in the group (b) is ( The number of atoms that become the element of the catalyst) / (b) The number of carbon atoms contained in the group of compounds = 〇·〇〇〇〇〇5 to 0·0015. [4] The method for producing carbon fibers by a gas phase method according to the above [3], wherein the ratio of the number of atoms of the element which becomes a catalyst in the raw material to the ratio of the number of carbon atoms contained in the group compound (the element which becomes a catalyst) The number of atoms) / (b) The number of carbon atoms contained in the group compound = 0.0000 1 to 0.001. [5] The method for producing a carbon fiber by a vapor phase method according to the above [1], wherein the ratio of the number of atoms which are elements of the catalyst in the raw material to the number of carbon atoms contained in the (a) group of compounds (the element which becomes a catalyst) Number of atoms) / (a) Number of carbon atoms contained in the group compound = 〇 · 0000 1 to ο.1· -10- (7) (7) 1311544 [6] Manufactured by a vapor phase method as described in [5] above The method of carbon fiber 'the ratio of the number of atoms which become a catalyst element in the raw material to the number of carbon atoms contained in the (a) group of compounds - (the number of atoms which become the element of the catalyst) / (a) The number of carbon atoms) = 0.000 1 to ο.1. [7] The method for producing carbon fibers by a gas phase method according to the above [1], wherein the ratio of the number of atoms which become a catalyst element in the raw material to the number of carbon atoms contained in the group (b) is a factor of the catalyst. The number of atoms) / (b) The number of carbon atoms contained in the group of compounds = 0.00 〇〇〇 5 to 0 _0 015, and the ratio of the number of atoms which become a catalyst element in the raw material to the number of carbon atoms of the (a) group of compounds (the number of atoms which become the element of the catalyst) / ( ( a ) The number of carbon atoms contained in the group of compounds) = 0.0000 1 to 0 [8] The method for producing carbon fibers by a gas phase method as described in the above [7] The ratio of the number of atoms that become a catalyst to the number of carbon atoms in the (b) group of compounds (the number of atoms that are the elements of the catalyst) / (b) the number of carbon atoms in the group of compounds = 0.00001 to 0.001 'The ratio of the number of atoms that become a catalyst in the raw material to the number of carbon atoms in the (a) group of compounds (the number of atoms that are the elements of the catalyst) / (a) The number of carbon atoms in the group of compounds = 0.000 1 to 0.1 ° . [9] A method for producing carbon fibers by a gas phase method as in the above [1] The (a) group compound and the (b) group compound satisfy the ((a) group of carbon atoms contained in the group of compounds) / ((a) group compound-11 - (8) 1311544 containing carbon atoms + ( The ratio of the conditions of b) the number of carbon atoms contained in the group compound = 0.003 to 〇·5 is supplied to the heating zone of the reaction reactor. [10] The method for producing a carbon fiber by a vapor phase method according to the above [1], wherein the (a) group compound and the (b) group compound satisfy ((a) the number of carbon atoms in the group compound) / ((a) The number of carbon atoms contained in the group compound + (b) The number of carbon atoms in the group of compounds) = 〇. The ratio of the conditions of 〇〇5 to 0.2 is supplied to the heating zone of the reactor. [1] The method for producing a carbon fiber by a vapor phase method according to any one of the above [1] to [1], wherein the (a) group compound is selected from the group consisting of carbon monoxide, carbon monoxide, a saturated aliphatic compound, and a saturated alicyclic compound. At least one compound in a group. [12] The method for producing a carbon fiber by a vapor phase method according to any one of the above [1] to [0], wherein the (a) group compound is selected from the group consisting of carbon monoxide, carbon dioxide, a saturated aliphatic hydrocarbon, a saturated aliphatic alcohol, and a saturated Aliphatic amines, saturated aliphatic thiols, saturated aliphatic esters, saturated aliphatic ethers, saturated aliphatic aldehydes, saturated aliphatic carboxylic acids, saturated alicyclic hydrocarbons, saturated alicyclic alcohols, saturated alicyclic amines, saturated alicyclic sulphur At least one compound of the group consisting of an alcohol, a saturated alicyclic ester, a saturated alicyclic ether, and a saturated alicyclic aldehyde 'saturated alicyclic carboxylic acid. [13] A method for producing a carbon fiber by a vapor phase method according to any one of [1] to [2], wherein the boiling point (1 atm) of the (a) group compound is less than 80 t. [Μ] A method for producing a carbon fiber-12-(9) 1311544 dimension by a gas phase method according to any one of [1] to [I2] wherein the (a) group compound is selected from the group consisting of carbon monoxide, carbon dioxide, methanol, ethanol, At least one compound of methane, ethane, propane and butane. [15] The method for producing a carbon fiber by a vapor phase method according to any one of [1] to [14] wherein the (b) group compound is at least one compound selected from the group consisting of aromatic hydrocarbons. [6] The method for producing a carbon fiber by a vapor phase method according to any one of the above [1] to [15] wherein the (b) group compound is selected from the group consisting of benzene, toluene, xylene, ethylbenzene, styrene, and A group of at least one compound. [17] The method for producing a carbon fiber by a gas phase method according to any one of the above [1] to [0], wherein the (a) group compound is at least selected from the group consisting of carbon monoxide, carbon dioxide, methanol, ethanol, and methane. A compound, wherein the (b) group compound is at least one compound selected from the group consisting of benzene, toluene and xylene. [18] The method for producing a carbon fiber by a vapor phase method according to any one of the above [1] to [17], wherein the raw material passes through a temperature range of 6 ° C or higher, less than 100 ° C and a temperature range of 1 〇 High temperature zone above 〇〇°c. [19] The method for producing carbon fibers by a gas phase method according to the above [18], wherein a residence time of a raw material composition containing a carbon compound and a catalyst and/or a catalyst precursor compound in a low temperature region is 0.5 seconds or longer. . [20] A method for producing a carbon fiber by a vapor phase method according to the above [18] or [19], wherein the (b) group compound is introduced into the high temperature region after introduction into the low temperature region. [21] A method for producing-13-(10) (10) 1311544 carbon fibers by a gas phase method according to any one of the above [1] to [0], wherein (a) a group of compounds, (b) are supplied in a gaseous state Group compounds and catalyst precursors in the heated zone. [2] The method for producing a carbon fiber by a vapor phase method according to any one of the above [1] to [21] wherein the catalyst precursor compound contains the third portion 5', 6 selected from the periodic table of the Group 18 element. 8, 9, 1 at least one metal of the Yi family. [23] A method of producing a carbon fiber by a vapor phase method according to any one of the above [1] to [22], wherein all or a part of the gas after the reaction is recycled. [24] The method for producing a carbon fiber by a vapor phase method according to any one of the above [1] to [2], wherein a carbon fiber 〇 [25] having an average fiber diameter of not more than nanometer is produced as in the above [1] to [24]. A gas phase carbon fiber produced by any of the manufacturing methods. [26] The vapor-phase carbon fiber of the above [25] wherein the residual catalyst content is 5 000 ppm by weight or less. [27] The vapor-process carbon fiber according to the above [25], wherein the residual catalyst content is 500 ppm by weight or less. According to the invention, the (a) group compound and the (b) group compound are used as both Carbon source, which can produce carbon fiber with high productivity with very little catalyst. [Embodiment] Hereinafter, the present invention will be described more specifically with reference to the drawings. -14- (11) (11) 1311544 (Carbon compound) In the method for producing a carbon fiber of the present invention, the carbon compound (carbon atom-containing compound) which is a carbon fiber raw material is selected from at least one compound of the following group (a) and selected a mixture of at least one compound from group (b). (a) Group: a carbon compound having no benzene ring structure in the molecule (b) Group: aromatic compound (a) The first condition of the group compound is a compound having no benzene ring in the molecule. Here, the benzene ring includes a condensed ring such as a benzene condensed naphthalene skeleton or an anthracene skeleton. A part of the benzene ring, which is substituted with oxygen, nitrogen, sulfur or the like, such as furan, pyridine or thiophene, which is also referred to as a benzene ring or a condensed ring, may not be included as a unit of the group (a). The carbon fiber is a system in which a carbon species decomposed by a carbon compound is dissolved or dissolved in a heating medium in a heating region, and is formed by precipitation. (a) The required functional group of the group compound is liable to become a carbon species which is easily hydrolyzed and decomposed and dissolved in the catalyst. Therefore, it is not suitable to dissolve a compound having a benzene skeleton directly in the molecule of the catalyst. Therefore, the group (a) is a compound of carbon monoxide, carbon dioxide, an aliphatic compound, an alicyclic compound or the like. Among them, aliphatic compounds and alicyclic compounds are aliphatic hydrocarbons, alicyclic hydrocarbons and derivatives thereof, and compounds having no benzene ring or condensed ring in the molecule. Aliphatic hydrocarbons and alicyclic hydrocarbons, and saturated ones are preferred. The reason why the saturator is preferred is that it is easy to become a carbon species which is easily hydrolyzed and decomposed and dissolved in the catalyst. Further, the group (a) may contain elements such as nitrogen and phosphorus 'oxygen, sulfur, fluorine, chlorine, bromine and iodine in addition to carbon and hydrogen. -15- (12) (12) 1311544 Further, in order to fully exert the effects of the present invention, (a) the group compound is preferably uniformly mixed with a catalyst or a catalyst precursor in a low temperature region. Therefore, the compound of the group (a) is uniformly mixed with the catalyst or the catalyst precursor in a low temperature region and in a state of being in a gaseous state or floating in the raw material gas, and it is preferable to be gasified by the gasification. It is preferable to sufficiently mix the compound of the (a) group and the (b) group to the heating region, and it is preferable to carry out the mixture of the (a) group and the (b) group compound in a vaporized state. Therefore, the '(a) group compound is preferably at a boiling point of less than 180 °C at 1 atm, less than 80 °C', and even better than 60 °C, and the best is less than 20C. Based on the above, examples of the (a) group of compounds include inorganic gases such as carbon monoxide and carbon dioxide; alkanes having 1 to 8 carbon atoms; and cyclic hydrocarbons having 3 to 8 carbon atoms. Preferred examples of the group (a) are inorganic gases such as carbon monoxide and carbon dioxide; toluenes such as ethane, propane, butane, pentane 'hexane, heptane and octane; cyclopropane and cyclopentane'. a cycloalkane such as hexane or the like. These hydrocarbons contain a derivative such as oxygen, nitrogen, sulfur, phosphorus, or halogen, such as an oxygen-containing compound such as methanol, ethanol, propanol or butanol, methyl mercaptan, methyl ethyl sulfide, and the like. A sulfur-containing aliphatic compound such as methyl mercaptan, a halogenated hydrocarbon such as chloroform, carbon tetrachloride or ethyl chloride may be used. More preferably, (a) a group of compounds, carbon monoxide, carbon dioxide, methanol, ethanol, methane, ethane, propane and butane, preferably (a) a group of compounds carbon monoxide, carbon dioxide, methanol, ethanol and methane. (b) Group aromatic compound means an aromatic hydrocarbon and a derivative thereof, and all compounds having a benzene ring. Aromatic hydrocarbons are preferred, but nitrogen and sulfur other than carbon and hydrogen -16- (13) 1311544, oxygen, sulfur, fluorine, chlorine, bromine, iodine and other elements are also possible. (b) The function of the group compound is deposited on the produced carbon fiber and carbonized to grow the carbon fiber in the radial direction. A compound having a benzene ring in the molecule is suitable. Preferred examples of the group (b) compound include benzene, toluene, xylene, styrene, ethylbenzene, and the like, and monocyclic aromatic hydrocarbons; polycyclic compounds having a condensed ring such as anthracene, naphthalene, anthracene, and phenanthrene. As the (b) group aromatic compound, a derivative containing oxygen, nitrogen, sulfur, phosphorus, halogen or the like, for example, a sulfur-containing aromatic compound such as benzenethiol or diphenyl sulfide, or the like can be used. A high-boiling aromatic compound can also be used, but it is advantageous in that it is preferably mixed with the compound of the group (a) to facilitate gasification, and a compound having a lower boiling point is preferred. Therefore, the compound of the group (b) is particularly preferably benzene, toluene, xylene, ethylbenzene, styrene, 5 or the like. The present invention is based on the use of the (a) group compound and the (b) group compound. When an aromatic compound having an alkyl group such as toluene or ethylbenzene is used as the group (b) compound, the decomposition of the alkyl group attached to the benzene ring in the heating region or before the temperature rise is also the same as the compound of the group (a). The effect. However, when ethylbenzene was supplied alone, as shown in Comparative Example 2, the effects of the present invention could not be achieved. In other words, the supply of a compound capable of providing the compounds of the (a) group and the (b) group as a result of decomposition or the like does not satisfy the requirements of the present invention. In the reactor having a portion heated to a temperature of about 600 to 130 ° C, the essential components of the present invention are supplied as a compound of (a) and a compound of (b). (a) The ratio of use of the group compound to the group (b) is 'the number of carbon atoms contained in the compound of ( -17 - (14) (14) 1311544 (a )) / (a) The number of carbon atoms + (b) The number of carbon atoms in the group of compounds) = 〇. 〇〇 1 to 0.9 is preferred. More preferably, ((3) the number of carbon atoms contained in the group of compounds) / (a) the number of carbon atoms in the group compound + the number of carbon atoms in the compound of the group (b) = 0.003 to 0.5. More preferably, it is (a) the number of carbon atoms contained in the group compound / (a) the number of carbon atoms contained in the group compound + (b) the number of carbon atoms contained in the group compound) = 0.005 to 0.2. (a) The addition of a small amount of the group compound has an effect. When it is excessively added, the non-fibrous solid component tends to be produced, and the fiber ratio is lowered. On the other hand, a large amount of carbon monoxide or the like is used as the (a) group compound, productivity is not improved, and the yield is extremely low. Therefore, the above range is preferred. For example, (a) group compound ethylene is continuously supplied to the heated zone of the reactor at a rate of 1 _ 2 〇 millimoles per minute at a rate of 1 2 2 mM millimoles per minute of ethylene (a) group compound The supply rate of the number of carbon atoms contained is 毫.8 mmol/min (the number of carbon atoms of ethylene is 2', 4.4x2 = 〇.8), and the supply rate of the number of carbon atoms contained in the group (b) is 7 · 2 〇 旲 / min (the carbon number of benzene is ό, so 1.20x7 = 7.20) ' (a) The number of carbon atoms in the group compound / (( a ) The number of carbon atoms in the group of compounds + (b) The number of carbon atoms contained in the group of compounds) = (〇.8 (catalyst) In the present invention, the catalyst is required to promote the growth of carbon fibers. There is no special limit brake. The catalyst is, for example, IU PAC at 19 Class 18 element promoted in 1990-18- (15) 1311544 At least one metal selected from Groups 3 to 2 in the periodic table. Selected from the 3rd, 5th, 6th, 8th, 9th, and 1st It is preferred that at least one of the groups of metals is better, and iron, nickel, cobalt, rhodium, ruthenium palladium, platinum, and rare earth elements are particularly preferred. (Cerox precursor compound) The catalyst precursor compound refers to pyrolysis by heating. sometimes A compound which is supplied to the above catalyst by reduction. For example, the catalyst precursor compound bis(々5-cyclopentadiene) iron is pyrolyzed by heating to form catalytic iron particles. Therefore, the compound supplied with the above metal is suitable as a catalyst. a precursor compound, an example of a more specific catalyst precursor compound, which comprises a metal compound containing at least one element selected from the group consisting of Groups 3 to 12, in particular, selected from the group consisting of 3, 5, 6, 8, and 9, 1 The compound of at least one element of the group of the Yi people is preferably a compound containing iron, nickel, cobalt, ruthenium, rhodium, palladium, platinum and rare earth elements. The metal compound of at least one element of the group of 1 to 17 is used as a modifying component of a catalyst (so-called catalyst) to adjust the performance of the main component metal catalyst. (Carrier) The above catalyst and/or catalyst precursor, If necessary, it can also be carried on a carrier. The carrier is preferably a compound which is stable in the heating zone. Examples of these compounds include alumina, cerium oxide, zeolite, magnesia, titania, zirconia, graphite, activated carbon. , carbon fiber, etc. (Use of catalyst, etc.) -19 - (16) (16) 1311544 The amount of catalyst or catalyst precursor compound used is 'the number of atoms of the catalyst 713 (such as Fe) and the raw material carbon compound. The ratio of the carbon mole number (that is, the number of all carbon atoms in the raw material such as a carbon compound) is preferably 0.000005 to 0.0015, and the 0.00001 to o.ool is better, 〇.0001 to 0.0005 is more preferable, and 0.0002 to 0.0004 is optimum. Less than 0·000005, the catalyst is insufficient, the number of fibers is reduced, and the fiber diameter is increased, so it is not good. When the ratio is more than 0 · 0 0 1 5, not only is it not squeezed, but coarse catalyst particles having no catalyst function are mixed into the fiber, which is not preferable. In the calculation of the weight ratio of all carbon atoms in the above raw materials, the calculation of the molar number of all carbon atoms means that not only the carbon compound but also the carbon atom derived from the additive component "solvent" such as a catalyst precursor compound, a promoter, or a carrier. The ratio of the number of atoms which are elements of the catalyst to the number of carbon atoms contained in the (a) group of compounds is (the number of atoms which are elements of the catalyst) / ((a) the number of carbon atoms contained in the group compound) = 0.00001 to The range of 0.1 is better. More preferably, (the number of atoms which become an element of the catalyst) / (a) the number of carbon atoms contained in the group compound = 0.0001 to 0.1. Particularly preferred is (the number of atoms which become an element of the catalyst) / ((a) the number of carbon atoms in the group compound) = 0.001 to 0.01. When the amount of the catalyst (a) group is too large, the catalyst in the low temperature region does not function (a) the group compound is increased. When the catalyst does not work and directly reaches the high temperature, the (a) group of compounds does not participate in the formation of the fiber 'growth, and the large amount thereof becomes a non-fibrous solid product such as a spherical shape. When the amount of the catalyst (a) group compound is too small, the aggregation of the catalyst cannot be sufficiently suppressed, the effective utilization rate of the catalyst is deteriorated, and the fiber yield is reduced. Sometimes, in the high temperature region, the (b) group compound is unfabricated for fiber growth. -20- (17) (17) 1311544 If a spherical solid product is mixed. The ratio of the number of atoms that are elements of the catalyst to the number of carbon atoms contained in the (b) group of compounds is (the number of atoms that are the elements of the catalyst) / (( b ) the number of carbon atoms contained in the group of compounds) = 〇. The range of 000005 to 0,0015 is preferred. More preferably, (the number of atoms which become an element of the catalyst) / (b) the number of carbon atoms in the group compound = 0.00001 to 0·001' is preferably (the number of atoms which become an element of the catalyst) / ( (a) The number of carbon atoms in the group compound is 0_00005 to 0.0〇1. Excessive compounding with respect to the catalyst (15) group rapidly decomposes in the high temperature region (b) and the carbonized fiber grows to form a non-fibrous solid product such as a spherical shape. When the amount of the compound (b) is too small, the carbon fiber generated is insufficiently grown, and the yield cannot be improved, and the productivity is low. The ratio of the number of atoms which become a catalyst element in the raw material to the number of carbon atoms contained in the (b) group compound is (the number of atoms which are elements of the catalyst) / (b) the number of carbon atoms in the group compound = 〇 .000005 to 0·0015' and the ratio of the number of atoms which become a catalyst element in the raw material to the number of carbon atoms contained in the (a) group of compounds (the number of atoms which become the element of the catalyst) / (a) Group compound The number of carbon atoms is limited to 〇·〇0001 to ο·1. Further, the ratio of the number of atoms which are elements of the catalyst in the raw material to the number of carbon atoms contained in the group (b) is (the number of atoms which are elements of the catalyst) / (b) the number of carbon atoms in the group of compounds) =〇.〇〇〇01 to 0.001' and the ratio of the number of atoms which become a catalyst element in the raw material to the number of carbon atoms contained in the (a) group of compounds (the number of atoms which become the element of the catalyst) / ( (a) The number of carbon atoms contained in the group compound) = 0.0001 to 〇. 丨 is more preferable. -21 - (18) (18) 1311544 (Method of supplying raw materials) There is no special restriction on the method of supplying raw materials. The (a) group compound, the (b) group compound, the catalyst and/or the catalyst precursor compound may be supplied in a gaseous state by partial gasification, or a part or all of them may be supplied in a liquid state. Within these compounds, the (a) group of compounds and the catalyst and/or catalyst precursor compound may be supplied first, and the (b) group of compounds may be supplied in the middle of the reaction system, but it is preferred to supply them simultaneously. However, a preferred embodiment may be to supply (a) a group of compounds with a catalyst and/or a catalyst precursor compound in a low temperature region, and to supply (b) a group of compounds to a high temperature region. (a) When the mixture of the group compound and the group (b) is more insufficient than the carrier gas shown below, the reaction system may have a lower concentration of the (a) group compound and (b) a lower concentration of the group compound. The effect of (a) group compounds is diminished. Therefore, it is preferred that the raw materials are vaporized before being introduced into the heating zone to be sufficiently mixed with the gaseous materials, and then supplied to the heating zone. (Carrier gas) When the carbon fiber is produced by the vapor phase method of the present invention, a carrier gas is preferably used in addition to these components. . The carrier gas may be hydrogen, nitrogen, ammonia, argon, helium or a mixed gas of these. However, a gas such as oxygen (i.e., oxygen in a molecular state) such as air is not suitable. The catalyst precursor compound used in the present invention is sometimes in an oxidized state, and it is preferred that the carrier gas is a hydrogen-containing gas. Therefore, the preferred carrier gas contains 1% by volume or more of hydrogen, more preferably 30% by volume or more, and more preferably _85% by volume or more, for example, 1% by volume of hydrogen or NB-(19) diluted with nitrogen. (19) 1311544 Hydrogen gas. (Sulfur compound) When the carbon fiber is produced by the vapor phase method of the present invention, a sulfur compound having an effect of controlling the carbon fiber diameter can be used. A compound such as sulfur, thiophene or hydrogen sulfide may be supplied in a gaseous state or dissolved in a solvent. It is of course also possible to use the (a) group compound, the (b) group compound, the sulfur-containing substance in the catalyst precursor compound. The total number of moles of sulfur to be supplied is preferably 1 〇〇〇 times the number of moles of the catalyst, and is preferably 1 〇〇 or less, more preferably 1 〇 or less. If the amount of sulfur supplied is too large, it is uneconomical, or it is also a cause of hindering the growth of carbon fibers. (Synthesis of Carbon Fiber) The carbon fiber synthesis by a vapor phase method is carried out by supplying the above-described raw material and, if necessary, a carrier gas to a heating zone and contacting it under heating. The reactor (heating furnace) is not particularly limited if it has a specific residence time and heating temperature, and the vertical or horizontal tubular furnace is better in the supply of raw materials and the retention time. The temperature of the heating zone varies with the carbonization used. The variety of things varies greatly. It is generally preferred to be below 500 ° C above 1 500 ° C below 800 ° C and above 1 3 5 0 ° c or less. If the temperature is too low, it does not grow into carbon fibers. If it is too high, it does not grow into carbon fibers, or only coarse fibers. In the present invention, the (a) group compound and the (b) group compound are used as the carbon source. (a) Group compounds and (b) group compounds contribute to the temperature at which carbon fibers are produced and grown. Therefore, there is no particular limitation, and the temperature of the heating zone is -23-(20) (20) 1311544, and it is preferred that the group (b) compound acts after the low temperature zone in which the group (a) compound acts. High temperature zone. In the two temperature zones, the temperature distribution has a low temperature zone and a high temperature zone two heating zones or a low temperature zone - the high temperature zone has a slope 'temperature gradually becomes higher. The low temperature zone (a) group compound is effective in the temperature zone in which the catalyst acts, preferably 6001 to 1 °C, preferably 700 ° C to 1000 ° C. When the temperature is too low, (a) the group compound does not act by the catalyst or the reaction rate is slow even if the reaction rate is slow, and the carbon fiber cannot be sufficiently formed. When the temperature is too high, (a) group • The compound is agglomerated by a large amount of catalyst before the catalyst acts. The effective utilization rate of the catalyst is lowered, and a product other than the state of fiber growth, for example, a spherical product is produced in a large amount. The high temperature zone (b) group compound acts efficiently on the carbon fiber, so that the temperature range in which the carbon fiber grows is preferably 1 〇〇〇 ° c to 15 〇〇 ° c, and 1 〇〇〇 ° c to 1 3 5 ot good. If the temperature is too low, the (b) group of compounds does not decompose and does not contribute to fiber growth. When the temperature is too high, (b) the group compound is rapidly decomposed, and a product other than the fiber growth state, for example, a spherical product is produced in a large amount. The residence time in the low temperature zone is preferably 0.1 second or more, more preferably 0.5 second or more. The better is 1 _ leap seconds or more. If the time is too short, carbon fiber may not be formed sufficiently. The residence time in the high temperature zone is preferably in the range of 0.000 1 second to 60 seconds, more preferably 0_001 to 30 seconds, and most preferably 1 to 15 seconds. If the residence time is too short, the carbon fiber does not grow, and if it is too long, only coarse fibers are sometimes obtained. The present invention can produce carbon fibers in a high yield and high productivity at a short residence time, and the residence time is too long to be poor. The residence time is adjusted by the length of the heating zone and the carrier gas flow rate. There are many different types of reaction devices and carbon compounds used in the -24 - (21) 1311544. If the residence time is too short, the carbon fiber does not grow, and if it is too long, only coarse fibers are sometimes obtained. In the present invention, the total residence time of the low temperature zone and the high temperature zone, that is, the residence time of the temperature range of 6 〇〇 or more may be 0.1 second to 30 seconds, preferably 0. 5 seconds to 30 seconds, 1.0 second to 1 6 seconds is better. The residence time in the temperature range above 6 °C is that the reaction gas is heated, and the temperature is raised from the temperature in the low temperature region exceeding 60 °C to the temperature in the high temperature region, and then cooled down to 60 °C. The residence time in the low temperature zone is from 600 °C over the temperature rise to over 100 °C. The residence time in the high temperature zone is longer than 1 〇 〇 〇 I and then cooled down to below 1000 °C. The reaction in the low temperature zone and the reaction in the high temperature zone can also be carried out separately. At this time, the residence time in the low temperature zone is 600 ° C which exceeds the reaction in the low temperature zone, is kept below 1 000 ° C and falls to 600 ° C, and then exceeds 600 ° when the temperature rises in the high temperature zone reaction. c up to the sum of the time beyond 100CTC. The total residence time of the low temperature zone and the high temperature zone is the sum of the reaction gas at a time of 60 (TC or more) in the case of a low temperature zone reaction and a high temperature zone reaction. The carbon fiber formation reaction is usually carried out in a reaction tube. At this time, if the flow rate is constant, the residence time can be adjusted by the change of the flow rate (change of the reaction tube diameter) or the change of the length of the heating belt. The time in the high temperature zone is extremely long, and (b) the reaction of the group compound is almost completely decomposed. The main component of the carbon compound in the gas is methane 'ethylene. When the oxygen gas contains an oxygen compound, carbon monoxide and carbon dioxide are added thereto. (b) The main component of the gas is decomposed when the decomposition of the group compound is incomplete -25 - (22 (22) 1311544 is the same as (1) above, and all or part of the gas after the reaction is directly supplied to the overheated region either directly or via the addition of the (a) group compound and/or the (b) group compound. It can be recycled and reused. When the gas after the reaction is circulated and reused, the amount of the (a) group compound and the (b) group compound in the raw material are contained in the gas for recycling and reuse. The amount of the reaction device is the sum of the amount of addition. One of the reaction devices is, for example, Fig. 2. In this case, the heater 2 - 1 ' is provided with a carrier gas introduced therein, (a) a group of compounds, (b) a group of compounds, and a catalyst or catalyst. The pipeline of the precursor compound. The lower part has a container for trapping the generated carbon fiber. Using this device, the heater 2-1 is heated to a specific temperature in the high temperature zone, and the reaction gas introduced into the reaction furnace reaches a specific temperature in the high temperature zone from room temperature. It is sufficient to satisfy the above conditions by adjusting the flow rate of the reaction gas through the residence time 1 of the low temperature zone, etc. In the present invention, it is preferable to have a difference in the temperature range of the low temperature zone and the high temperature zone, so that it can also be used as shown in Fig. 3. It is equipped with a reaction device capable of independently controlling the heaters 2 - 1 and 2 - 2 of these temperature zones. At this time, the heater 2 - 1 is heated to a specific temperature in the low temperature zone, and the heater 2 - 2 is heated to a high temperature range. At a specific temperature, a mixed gas containing a carrier gas, a group (a) group compound, a group (b) compound, and a catalyst or a catalyst precursor compound is passed through a reaction apparatus to obtain a carbon fiber. In FIG. 3, the heater 2 - 1 and heater 2 - 2 series are set continuously, but the heater can be set separately, after the heater 2 - 1 'after the gas temperature is lower than the temperature in the low temperature zone', the heater 2 - 2 is heated to High temperature zone. The invention is characterized in that the carbon source supplied is efficiently recovered by carbon fiber. The mechanism is basically that the (a) group of compounds are in contact with the catalyst to form fibers -26 - (23) (23) 1311544 'mainly (b) The group compound is a carbon source and is effectively thickened in the radial direction. Therefore, it is not suitable for the production of carbon fibers having an extremely small outer diameter such as a single wall or a double wall. It is very suitable for the production of coarse fibers. It is most suitable for the production method of carbon fibers having an average outer diameter of 10 nm or more, 50 nm or more, particularly 80 nm or more, and most preferably 100 nm or more. Here, the outer diameter of the carbon fiber can be determined, for example, by measuring the outer diameter of about 100 fibers by SEM photography. Alternatively, it can be calculated from the assumption that the BET specific surface area is a cylinder. With the present invention, the utilization efficiency of the catalyst or catalyst precursor can be significantly improved. That is, carbon fiber can be efficiently produced with a small amount of catalyst. The carbon fiber produced by the usual method has a catalyst (iron, etc.) of about 50,000 ppm by weight. In order to improve the physical properties of the carbon fiber to be produced, calcination (about 1 500 ° C) and graphitization under inert gas (200 to 300 ° C) may be applied. At this time, part of the catalyst iron is vaporized and evaporated, so that the amount of catalyst remaining in the carbon fiber after the graphitization treatment is lowered. On the other hand, by the production method of the present invention, the content of the catalyst in the carbon fiber can be made extremely low without being subjected to treatment such as calcination and graphitization. The catalyst content may be 5 (10) 0 P p or less in a state where no treatment such as calcination or graphitization is carried out, and a carbon fiber of 50,000 p p or less is preferably obtained under the preferable conditions. The graphitization treatment may not be necessary depending on the use. Further, in the method of the present invention, the average outer diameter of the obtained fiber tends to vary with the change in the ratio of the number of carbon atoms contained in the (a) group compound to the number of carbon atoms contained in the group (b). It is easy to say that (a) when the ratio of the number of carbon atoms in the group compound is increased, the fiber diameter becomes small. When the ratio is decreased, the fiber diameter becomes large. This presentation 'can be controlled by small changes in the conditions of the reaction equipment, and only the change in the composition of the carbon compound of the raw material can be controlled to control the average outer diameter of the carbon fiber -27-(24) 1311544. For example, carbon fibers having a fiber outer diameter of 80 to 150 nm can be produced very simply. EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. The reagents used in the following examples and comparative examples are as follows. [Pharmaceuticals] 1 · ( a ) Group of compounds carbon monoxide: Japanese oxygen (shares) Carbon dioxide: phase acetylene (shares) Methane: Takachiho Corporation (shares) Ethylene: Japanese oxygen (shares) Methanol: Wako Pure Chemical Industries Co., Ltd. Ethanol : 和光纯药工业(股) _ 2. (b) Group of compounds benzene: Wako Pure Chemical Industries Co., Ltd. Toluene: Wako Pure Chemical Industries Co., Ltd. Para-xylene: Wako Pure Chemical Industries Co., Ltd. Ethylbenzene: Heguang Pure Pharmaceutical industry (shares) 3. Catalyst precursor compound-28- (25) (25) 1311544 bis(77 5 -cyclopentadienyl) iron: Japanese ΖΕΟΝ (shares) 4. Other ingredients thiophene: Wako Pure Chemical Industries Co., Ltd. ) [Synthesis of carbon fiber] <Example 1 > a: Ethylene and b: Benzene The upright type having the reaction tube 1 made of quartz (the inner diameter of 3 mm, the outer diameter of 36 mm, and the heating zone length of about 400 mm) was used. In the furnace, the heating zone was heated to 1 250 °C in the N2 gas stream, and then the supply of N2 was cut off, and the carrier gas H2 was passed through the reaction tube at 1 standard liter/min. After the temperature is stabilized, ethylene ((a) group compound) is mixed with H2 in a gaseous state. Benzene ((b) group compound), bis(^5-cyclopentadienyl) iron and thiophene were dissolved and mixed, and the liquid was introduced into the gas heated to 200 °C in 10 minutes using the small pump with the introduction amount of Table 1. The chemicalizer 4 is vaporized and combined with a mixed gas of H2 & ethylene. Thus, all compounds are supplied to the reaction tube in a gaseous state. As a result of the reaction, a gray-colored spider nest deposit is formed between the bottom of the reaction tube and the trap. After the temperature is lowered, the deposit is recovered, and the amount of carbon is divided by the amount of carbon contained in the carbon compound used for the carbon recovery. rate. The spider nest-like product was observed with a whisk-type electron microscope. The results are shown in Table 1. The product has an average outer diameter of 150 nanometers of fibrous material, and the carbon recovery rate is 3 5 % °. At this time, the residence time of the low temperature zone of 600 ° C or less and less than 1 000 ° C is about 0-6 seconds, 60 0 The residence time in the °C temperature zone is about 3.7 seconds. -29- (26) (26) 13 Π 544 <Example 2> a: methane, b: benzene The reaction was carried out in the same manner as in Example 1 except that the substituted ethylene was changed to methane. The results are shown in Table 1. The product was a fiber with an average outer diameter of 150 nanometers. The carbon recovery was 35%. <Example 3> a: - Carbon oxide, b: benzene The reaction was carried out in the same manner as in Example 1 except that the substituted ethylene was changed to carbon monoxide. The results are shown in Table 1. The product was a fiber having an average outer diameter of 150 nm and a carbon recovery of 35%. <Example 4> a: Carbon dioxide, b: benzene The reaction was carried out in the same manner as in Example 1 except that the substituted ethylene was changed to carbon dioxide. The results are shown in Table 1. The product was a fiber having an average outer diameter of 150 nm and a carbon recovery of 35 %. <Example 5> a: Methanol, b; benzene The reaction was carried out as in Example 1 except that ethylene was not used, and benzene, bis(^3-cyclopentadienyl) iron and thiophene were dissolved in methanol. The results are shown in Table 1. The product is a fiber with an average outer diameter of 150 nanometers. Carbon recovery rate of 38% <Example 6> a: Ethanol, b; benzene The reaction was carried out as in Example 1 except that ethylene was not dissolved in a mixture of benzene, bis(々3-cyclopentadienyl) iron and thiophene. The results are shown in Table 1 of -30 - (27) (27) 1311544. The product is a fiber with an average outer diameter of 150 nanometers. Carbon recovery rate of 3 1 % <Example 7> a: Methanol, b; benzene The substituted benzene was changed to the reaction of Example 1 except for toluene. The results are shown in Table 1. The product was a fiber having an average outer diameter of 150 nm and a carbon recovery of 37%. <Example 8> a: Ethylene, b; styrene introduction amount was halved to the same manner as in Example 1, except that the reaction was carried out in the same manner as in Example 1. The results are shown in Table 1. The product was a fiber having an average outer diameter of 150 nm and a carbon recovery of 36%. <Example 9> a: methane, b; toluene The reaction was carried out in the same manner as in Example 1 except that the ethylene was replaced with methane and the benzene was replaced with toluene. The results are shown in Table 1. The product was a fibrous material having an average outer diameter of 150 nm and a carbon recovery of 37%. <Example 1 0 > a: methane, b; p-xylene Substituted ethylene was changed to methane' and the benzene was replaced with p-xylene to carry out the reaction according to the method of Example 1. The results are shown in Table 1. The product was a fibrous material having an average outer diameter of 150 nm and a carbon recovery of 35%. <Example 1 1 > a : - Carbon oxide, b: Benzene - 31 - (28) (28) 1311544 The reaction was carried out in the same manner as in Example 3 except that the amount of carbon monoxide was changed. The results are shown in Table 1. The product was a fiber with an average outer diameter of 150 nm and a recovery of 20%. <Example 1 2 > a : Carbon monoxide, b: benzene The reaction was carried out in the same manner as in Example 3 except that the amount of carbon monoxide was changed. The results are shown in Table 1. The product was a fiber with an average outer diameter of 150 nm and the carbon recovery was 27%. <Example 1 3 > a : methane, b: benzene The reaction was carried out in the same manner as in Example 2 except that the amounts of methane and benzene were changed. The results are shown in Table 1. The product was a fiber with an average outer diameter of 100 nm and had a carbon recovery of 24%. <Example 1 4 > a : methane, b: benzene The reaction was carried out in the same manner as in Example 2 except that the amounts of methane and benzene were changed. The results are shown in Table 1. The product was a fiber with an average outer diameter of 80 nm and the carbon recovery was 18%. <Example 1 5 > a : methane, b: benzene The reaction was carried out in the same manner as in Example 2 except for changing methane, bis(7/5-cyclopentadienyl)iron or thiophene. The results are shown in Table 1. The product was a fibrous material having an average outer diameter of 100 nm and a carbon recovery of 35 %. -32- (29) 1311544 <Example 1 6 > a : methane, b: benzene The reaction was carried out in the same manner as in Example 2 except that the amount of the compound was changed. The results are shown in Table 1. The fiber with an average outer diameter of 150 nanometers has a carbon recovery of 6 〇 %. <Comparative Examples 1, 2 > Using only benzene or ethylbenzene as the compound of group (b) without reaction, the reaction was carried out as in Example 1. The recovered solids were almost all spherical carbon fruits listed in Table 1. <Comparative Example 3 > In the case of a quartz reaction tube 1 (inner diameter: 31 mm, 36 mm, heating zone length: about 4 mm), as shown in Fig. 4, the vertical furnace 4, N2, bypass tube 5 Flowing through the 'one side of the heating zone to the temperature, and then cutting off the supply of N2' through the bypass pipe 5 in 1 standard liter / minute pipe flow overload gas H2. After the temperature was stabilized, the amount of ethylene in Table 1 was mixed with the carrier gas. Then, a portion of the carrier gas and the combined gas introduced by the bypass pipe 5, which has been fed in advance to the gasifier 4' which is heated to 7:5-cyclopentane to l4 °C, is divided into 3 3 ml/ The flow rate of one minute flows. The amount of thiophene introduced into the gasifier (raw material component) double (77 5 a calcined) iron and thiophene in a gaseous state combined with the mixed gas of carrier gas and ethylene and the bypass tube 5 ' The temperature at which all the compounds are supplied to the reaction tube vaporizer 4 in a gaseous state and the amount of carrier gas and ethylene to be injected are used to detect the amount of bis(〇5-cyclopentadiene pentene) which can be introduced into Table 1. In addition to the product system, the granules, the outer diameter of the gas is not reacted with the gas at a temperature of 1 2 5 0 °C in the reaction of the gaseous olefins, and the iron and ethylene are mixed with the cyclopentane, mixed; inside. Gas flow) iron-33- (30) (30) 1311544 Conditions use this condition. In this comparative example, since the solid bis(77 5 -cyclopentadienyl) iron is not dissolved, the liquid component (for example, benzene) supplied to the gasifier 4 is first. Double (7? 5-cyclopentane) The diene) iron is fed into the gasifier to sublimate it. Thiophene is a liquid, but not sufficient to dissolve bis(7/5-cyclopentadienyl) iron. The recovered solid components are almost all spheres, and some are fibrous.
-34 - 1311544 ί, 生成之碳固體成分的形狀 纖維徑150奈米左右之纖維狀物 纖維徑150奈米左右之纖維狀物 纖維徑150奈米左右之纖維狀物 纖維徑150奈米左右之纖維狀物 纖維徑150奈米左右之纖維狀物 纖維徑150奈米左右之織維狀物 纖維徑150奈米左右之繊維狀物 纖維徑150奈米左右之繊維狀物 繊維徑150奈米左右之纖維狀物 纖維徑150奈米左右之纖維狀物 纖維徑150奈米左右之纖維狀物 纖維徑150奈米左右之纖維狀物 纖維徑100奈米左右之纖維狀物 纖維徑80奈米左右之纖維狀物 纖維徑1〇〇奈米左右之纖維狀物 I纖維徑150奈米左右之纖維狀物 球狀物 i 球狀物 嵌 聲萆 i驾 雄* a _ 筢~ I W 碳回 收率 35% 35%」 I 34% 38% I | 38% j 31% : 36% 39% 37% 35% | 20% 27% 24% 18% 35% I 60% I 30% | 21% I !24% D/C 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 j 0.00003 0.00004 0.00006 0.00006 0.0006 丨 0.0007 j 0.00006 I 0.00006 I 0.003 I D/B I 0.0006 -1 0.0006 I | 0.0006 CD 〇 q ό 0.0006 <£> 〇 〇 〇 0.0006 | 0.0006 0.0006 0.0006 丨0.00006 0.00006 0.0001 0.0003 0.0007 1 0.0007 [0.00006 0.00006 I D/A 0.0006 : 0.0006 i 0.0006 1 0.0006 0.0006 ! 0.0006 0.0006 ! 0.006 0.0006 I 0.0006 丨 0.00006] 1 0.0001 0.0001 I0.00008 0.007 1 0.0035 I I 1 0.003 1 Α/+ (Α+Β) 0.09 0.09 0.09 0.09 0.09 0.09 i 0.09 0.01 0.09 0.09 LO d CO d U0 d 00 d 0.09 丨 0.02 〇 〇 噻吩導入量 毫莫耳/分鐘 0.0007 0.0007 0.0007 0.0007 0.0007 0.0007 i 0.0007 0.0007 0.0007 0.0007 0.0007 0.0007 0.0007 0.0007 0.01 '0.005 [0.0007 0.0007 0.016 |雙U5-環戊二 m m < ^ » ^ 變s 涯蝴 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.006 '0.0028 I 0.0005 ,0.0005 0.020 ⑼群 導入量 毫莫耳/分鐘 CO CO T— CO T- CO τ— CO cq τ~ T- T— CO τ~ τ— 〇 T- CO CO τ— d 0.27 C0 T— CD CO r~ σ I 化合物 1 i 擀 擀 擀 淋 擀 擀 浒 & |對二甲苯i 擀 擀 擀 擀 枨 齡 乙苯 I 丨⑻群 導入量 毫莫耳/分鐘 寸 d 00 d CO 〇 CO ό 00 〇 ό 寸 ό 0.04 CO d 00 d 〇 〇0 Ο — p — CD 00 d 00 〇 I I 〇 — 化合物 发 KI 遯 〇 〇 I C〇2 I I乙醇i I乙烯| 乙烯 甲烷 I甲烷I 〇 〇 〇 ο i甲烷 |甲烷| 5S & I ! !乙烯 I 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例10 實施例11 實施例12 |實施例13j 實施例14 實施例15 實施例16 比較例1 |比較例2 I 比較例3 裁fr陛磐杓釦宏盈仞Joi (q) ： a s屮蛏31jN<fliE「4<πΛ3ί (e)： <-34 - 1311544 ί, The shape of the carbon solid component is about 150 nm. The fiber diameter is about 150 nm. The fiber diameter is about 150 nm. The fiber diameter is about 150 nm. The fibrous fiber has a fiber diameter of about 150 nm. The fiber diameter is about 150 nm. The fiber diameter is about 150 nm. The fiber diameter is about 150 nm. The diameter of the fiber is about 150 nm. Fibrous fiber diameter of about 150 nm, fibrous fiber diameter of about 150 nm, fibrous fiber diameter of about 150 nm, fibrous fiber diameter of about 100 nm, fiber diameter of 80 nm or so Fibrous fiber diameter of about 1 nanometer, fiber I, fiber diameter of about 150 nanometers, spherical ball i, ball-shaped sound, 驾i driving male * a _ 筢~ IW carbon recovery rate 35 % 35%" I 34% 38% I | 38% j 31% : 36% 39% 37% 35% | 20% 27% 24% 18% 35% I 60% I 30% | 21% I !24% D /C 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 0.00005 j 0.00003 0.00004 0.00006 0.00006 0.0006 丨0.0007 j 0.00006 I 0.00006 I 0.003 ID/BI 0.0006 -1 0.0006 I | 0.0006 CD 〇q ό 0.0006 <£> 〇〇〇0.0006 | 0.0006 0.0006 0.0006 丨0.00006 0.00006 0.0001 0.0003 0.0007 1 0.0007 [0.00006 0.00006 ID/A 0.0006 : 0.0006 i 0.0006 1 0.0006 0.0006 ! 0.0006 0.0006 ! 0.006 0.0006 I 0.0006 丨0.00006] 1 0.0001 0.0001 I0.00008 0.007 1 0.0035 II 1 0.003 1 Α/+ (Α+Β) 0.09 0.09 0.09 0.09 0.09 0.09 i 0.09 0.01 0.09 0.09 LO d CO d U0 d 00 d 0.09 丨0.02 〇〇thiophene introduction amount millimoles / minute 0.0007 0.0007 0.0007 0.0007 0.0007 0.0007 i 0.0007 0.0007 0.0007 0.0007 0.0007 0.0007 0.0007 0.0007 0.01 '0.005 [0.0007 0.0007 0.016 | Double U5-cyclopentane Mm < ^ » ^ change s ya butterfly 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.0005 0.006 '0.0028 I 0.0005 ,0.0005 0.020 (9) Group introduction amount millimoles / minute CO CO T - CO T- CO τ — CO cq τ~ T- T— CO τ~ τ— 〇T- CO CO τ— d 0.27 C0 T— CD CO r~ σ I Compound 1 i 擀擀擀擀擀浒 擀擀浒 & | p-xylene i 擀擀擀擀枨 age ethylbenzene I 丨 (8) group introduction amount millimoles / minute inch d 00 d CO 〇CO ό 00 〇ό inch ό 0.04 CO d 00 d 〇〇 0 Ο — p — CD 00 d 00 〇II 〇 — Compound KI 遁〇〇IC〇2 II Ethanol i I Ethylene | Ethylene Methane I Methane I 〇〇〇ο i Methane | Methane | 5S & I ! ! Ethylene I Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Example 12 | Embodiment 13j Example 14 Example 15 Example 16 Comparison Example 1 |Comparative Example 2 I Comparative Example 3 裁fr陛磐杓扣宏盈仞Joi (q) : as屮蛏31jN<fliE“4<πΛ3ί (e): <
srfiss »IRl%ig®® 链：α 0^00 g £ .. u -35 - (32) (32)1311544 【圖式簡單說明】 第1圖係用來以氣相法製造碳纖維之橫臥式反應裝置 之一般例的示意圖。 第2圖係用來以氣相法製造碳纖維之具有一爐之直立 型反應裝置的一例之示意圖。亦係實施例1至1 6、比較例1 、2的以氣相法製造碳纖維之反應裝置的示意圖。 第3圖係用來以氣相法製造碳纖維之具有二爐的直立 式反應裝置之一例的示意圖。 第4圖係比較例3中以氣相法製造碳纖維之反應裝置的 示意圖。 〔主要元件對照表〕 1 石英製反應管 2—1 加熱器1 2—2 加熱器2 3 捕集器 4 氣化器 5 旁通管Srfiss »IRl%ig®® chain: α 0^00 g £ .. u -35 - (32) (32)1311544 [Simplified illustration] Figure 1 is a horizontal cross-section for the production of carbon fiber by gas phase method. A schematic diagram of a general example of a reaction apparatus. Fig. 2 is a schematic view showing an example of an upright type reaction apparatus having a furnace for producing carbon fibers by a gas phase method. A schematic diagram of a reaction apparatus for producing carbon fibers by a gas phase method of Examples 1 to 16 and Comparative Examples 1 and 2 was also carried out. Fig. 3 is a schematic view showing an example of an upright reaction apparatus having two furnaces for producing carbon fibers by a gas phase method. Fig. 4 is a schematic view showing a reaction apparatus for producing carbon fibers by a gas phase method in Comparative Example 3. [Main component comparison table] 1 Quartz reaction tube 2-1 Heater 1 2-2 Heater 2 3 Trap 4 Gasifier 5 Bypass