1248483 玖、發明說明 【發明所屬之技術領域】 本發明係有關於一種氣相成長碳纖維（Vapor-Grown Carbon Fibers)的反應裝置，特別是有關於一種具有高熱 傳導效率，並可防止碳纖維附著於内管壁上之氣相成長 碳纖維的反應裝置。 【先前技術】 以氣相法生成之碳纖維具有獨特之洋蔥環狀 (Onion-Ring)微結構、高長徑比（Aspect rati〇)、高導熱係 數、低電阻係數、低熱膨脹係數、高強度、高彈性、高耐 腐蝕性等優良的材料特性。加上，使用氣相法來製造碳纖 維可藉由熱處理而獲得近乎單結晶之石墨構造，故能形成 理想的層壁碳管，其導電性相當良好，導熱性更優於銅或 鋁等南導熱性材料。氣相法生成之碳纖維的成功研發，使 長期以來由PAN、Pltch等有機系碳纖維（〇]?(：：17)技術主導 的碳纖維領域，增添了一種相當重要的技術。 。氣相法生成之石反纖維的技術主要係以低碳烴爲原料 (反源）在還原性載氣（H2)氣氛中高溫熱解，通過如鐵、 鎳、鈷等過渡金屬的超細微粒爲晶核的特殊催化作用，而 直接生成氣相成長碳纖維，其反應溫度係介於_。卜 I氣相成長^纖維的製備具有獨特優勢：即製 備工藝簡單，盔f：彳隹p “ ^ 、 … 仃、、方、、糸、預氧化、碳化等opcf技術 所必需的製造步驟，可亩 乂置接由廉彳貝的低碳烴類通過高溫 1248483 熱解，催化生成碳纖維' 請麥照第1A圖和第1B圖，其為繪示習知之氣相成 長碳纖維之反應裝置的結構示意圖，其中習知之氣相成長 石反纖維的反應裝置係由反應管結構和加熱器5〇所組成， 而反應管結構可單獨由外管4〇(如第1A圖所示）或由内管 30裝入外管40中所形成（如第1B圖所示）。 如第1A圖所示之反應管結構，原料氣體係自安裝於 外管40之一端的進氣導管1〇進入外管4〇中，而加熱器 50所產生的熱能，經外管40傳遞至原料氣體、載氣的混 合氣體中，以提升混合氣體的溫度，來使原料氣體和載氣 產生南溫熱解生成碳纖維。然後，所產生之碳纖維落入收 集槽60中。然、而，以此方式進行生產時，管壁附近温度 較咼，但反應管中心溫度加熱不易，因此只適用於較小口 徑之反應管，不適合於大量生產。且管壁上經常會附著有 碳纖維，使得產率降低，且需時常停機清理而不利於連續 生產。 如第1B圖所示之反應管結構，原料氣體自安裝於夕 管40之一端的進氣導管1〇進入外管4〇中，載氣 安裝於外管40之一端的進氣口 20進入外管4〇中，惰个 氣體由外管40下方進入做為引導氣體。原料氣體和載_ 混合後，進入内管30,其中加熱器5〇所產生的熱能，衾 外管40傳遞至内管30,再傳遞至原料氣體、載氣和惰小 氣體的混合氣體中，以提升混合氣體的溫度，來使原料4 體和載氣產生高溫熱解而生成碳纖維。然後，所產生之石」 1248483 纖維落入收集槽60中。一般，内管3〇和外管4〇之間通 2惰性氣體當引導氣體（Guide Gas)，以加強内管3〇和外 管40之間的熱傳導效率。然、*，由於引導氣體的熱傳導 係數不高，故加熱器50對混合氣體的加熱效率不佳，無 ，有效地利用加熱器50所提供之熱能，而且碳源在惰： 2體中裂解產生氣相成長碳纖維不如在純還原載氣（H2) 氣氛下成長。此外，習知反應裝置之内f 3〇的管壁上經 常會附著有碳纖維，使得產率降低，不利於連續生產，更 造成清理上相當大的困擾，而浪費許多人力物力。 因此’非常需要發展一種氣相成長碳纖維的反應裝 置，藉以有效地利用加熱器所提供之熱能，並防止碳纖 維在内管的管壁上生成，因而提高產率，且易於清理反應 管，以減少人力物力的浪費。 【發明内容】 本發明的目的就是在提供_種氣相成長碳纖維的及 應裝置’藉以大幅地提升加熱器所提供之熱能的有效利 用率’而降低生產成本。 本發明的又一目的就是在提供一種氣相成長碳纖维 的反應裝置，藉以將載氣轉向至反應管的中心，來辦加 載氣與原料氣體混合之效果，同時防止碳纖維在^壁 生成’因而提高產率’ ϋ節省清理反應管的時間。 的反目的就是在提供—㈣相成長碳纖維 的反應裝置，错以有效地利用整體加熱能量，並能使氣體 1248483 在反應官之兩端冷卻，而在反應管中間部位受熱反應的 良好效果。 根據本發明之上述目的，提出一種氣相成長碳纖維的 反應裝置。按本發明的内容，此氣相成長碳纖維的反應裝 置至少包括··垂直式反應管結構和加熱器。其中，垂直式 反應官結構係由外管和内管所組成。内管係位於外管内 部’内官上端設有進氣導管藉以通入原料氣體，内外管間 有導熱填充物，並有隔板分隔成上下内管，其中上方内 管為第一内管，下方内管為第二内管，第一内管的一端對 齊外官的一端，第一内管的下部管壁具有複數個第一孔 洞，而第一内管與外管之間具有進氣口，藉以通入第二載 氣來冷部外管和第一内管的一端。第二内管係位於第一内 管的下方，而第二内管的上部管壁具有複數個第二孔洞。 第一内管與外管之間，及第二内管與外管之間的填充部分 填充有熱導材料，此填充部分所對應之第二内管的長度大 於第二孔洞所對應之第二内管的長度，而熱導材料下方之 外管具有第二進氣口，藉以通入第一載氣。另外，加熱器 的兩端與外官的兩端之間分別具有距離，且加熱器係對應 於部分之第一内管和部分之第二内管，藉以對部分之外管 力口熱。 因此，應用本發明，可大幅地提升加熱器所提供之 熱把的有效利用率，而降低生產成本；可增加載氣與原 料氣體混合之效果，同時防止碳纖維在管壁生成，因 而提高產率，且易於清理反應管；可有效地利用整體加熱 1248483 能量、，並產生氣體在反應管之兩端冷卻，而在反應管之 中間受熱反應的良好效果。 【實施方式】 本發明係在垂直式反應管結構之内管的部份管壁 設置複數個孔洞，以及在内管和外管間填充熱導材 料，藉以增加載氣與原料氣體的混合效果；防止碳纖 維在内管的管壁上生成；以及提高熱傳導效率。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reaction apparatus for Vapor-Grown Carbon Fibers, and more particularly to a method having high heat transfer efficiency and preventing carbon fibers from adhering thereto. A reaction device for vapor-grown carbon fibers on the tube wall. [Prior Art] Carbon fiber produced by gas phase method has a unique Onion-Ring microstructure, high aspect ratio (Aspect rati〇), high thermal conductivity, low electrical resistivity, low thermal expansion coefficient, high strength, Excellent material properties such as high elasticity and high corrosion resistance. In addition, the use of gas phase method to produce carbon fiber can obtain nearly monocrystalline graphite structure by heat treatment, so it can form an ideal layer wall carbon tube, which has relatively good conductivity and better thermal conductivity than copper or aluminum. Sexual material. The successful development of carbon fiber produced by gas phase method has added a very important technology to the field of carbon fiber, which has long been dominated by organic carbon fiber (〇:?) technology such as PAN and Pltch. The technology of stone anti-fibres is mainly based on low-carbon hydrocarbons as raw materials (anti-source) pyrolysis in a reducing carrier gas (H2) atmosphere, and special nucleation of ultrafine particles such as iron, nickel, cobalt and the like as transition crystals. Catalytic action, and directly generate vapor-grown carbon fiber, the reaction temperature is between _. I I vapor phase growth fiber preparation has a unique advantage: the preparation process is simple, the helmet f: 彳隹p " ^, ... 仃, The manufacturing steps necessary for the opcf technology such as square, ruthenium, pre-oxidation, and carbonization can be placed in the low-carbon hydrocarbons of Lianbei mussels through pyrolysis of high temperature 1244883 to catalyze the formation of carbon fiber. 1B is a schematic view showing the structure of a conventional gas phase growth carbon fiber reaction device, wherein the conventional gas phase growth stone anti-fiber reaction device is composed of a reaction tube structure and a heater 5〇, and the reaction tube structure can be It is formed by the outer tube 4〇 (as shown in Fig. 1A) or the inner tube 30 is loaded into the outer tube 40 (as shown in Fig. 1B). The reaction tube structure as shown in Fig. 1A, the raw material gas system The intake duct 1A installed at one end of the outer tube 40 enters the outer tube 4, and the heat energy generated by the heater 50 is transmitted to the mixed gas of the material gas and the carrier gas through the outer tube 40 to raise the mixed gas. The temperature is such that the raw material gas and the carrier gas are pyrolyzed to form carbon fibers at a south temperature. Then, the produced carbon fibers fall into the collecting tank 60. However, when the production is carried out in this manner, the temperature near the tube wall is relatively low, but The temperature at the center of the reaction tube is not easy to heat, so it is only suitable for reaction tubes of smaller diameter, which is not suitable for mass production. Carbon fiber is often attached to the tube wall, which reduces the yield and requires frequent shutdown to facilitate continuous production. In the reaction tube structure shown in FIG. 1B, the material gas enters the outer tube 4〇 from the intake duct 1安装 installed at one end of the outer tube 40, and the air inlet 20 installed at one end of the outer tube 40 enters the outer tube. 4 ,, the inert gas is under the outer tube 40 The inlet gas is used as a guiding gas. After the raw material gas and the carrier _ are mixed, the inner tube 30 is entered, wherein the heat generated by the heater 5 is transferred to the inner tube 30 and then transferred to the raw material gas, the carrier gas and the small inertia. In the mixed gas of the gas, the temperature of the mixed gas is raised to cause high-temperature pyrolysis of the raw material 4 and the carrier gas to form carbon fibers. Then, the generated stone "1248483" fibers fall into the collecting tank 60. Generally, the inner tube 3 inert gas is passed between the outer tube and the outer tube 4 to guide the gas (Guide Gas) to enhance the heat transfer efficiency between the inner tube 3 and the outer tube 40. However, *, because the heat transfer coefficient of the guiding gas is not high, Therefore, the heating efficiency of the heater 50 to the mixed gas is not good, and the heat energy provided by the heater 50 is effectively utilized, and the carbon source is cracked in the inert body: the vapor phase growth carbon fiber is inferior to the pure reduction carrier gas (H2). Grow in the atmosphere. In addition, the carbon fiber is often attached to the wall of the f 3 习 in the conventional reaction device, so that the yield is lowered, which is disadvantageous for continuous production, and causes considerable trouble in cleaning, which wastes a lot of manpower and material resources. Therefore, it is very necessary to develop a reaction device for vapor-grown carbon fiber, thereby effectively utilizing the heat energy provided by the heater and preventing the carbon fiber from being generated on the inner wall of the inner tube, thereby improving the yield and easily cleaning the reaction tube to reduce Waste of human and material resources. SUMMARY OF THE INVENTION An object of the present invention is to reduce the production cost by providing a gas phase-increasing carbon fiber (s) device to greatly increase the effective utilization rate of heat energy provided by the heater. Still another object of the present invention is to provide a reaction apparatus for vapor-grown carbon fibers, whereby a carrier gas is diverted to a center of a reaction tube to effect mixing of a carrier gas and a material gas, and at the same time prevent carbon fibers from being generated in the wall. Increase the yield' ϋ save time in cleaning the reaction tube. The opposite objective is to provide a (four) phase-growth carbon fiber reaction device that effectively utilizes the overall heating energy and allows the gas 1248483 to be cooled at both ends of the reactor and is thermally reacted in the middle of the reaction tube. According to the above object of the present invention, a reaction apparatus for vapor-grown carbon fibers is proposed. According to the present invention, the reaction apparatus for the vapor-grown carbon fiber includes at least a vertical reaction tube structure and a heater. Among them, the vertical reaction structure is composed of an outer tube and an inner tube. The inner tube is located inside the outer tube. The upper end of the inner tube is provided with an air inlet duct for introducing raw material gas, and the inner and outer tubes are provided with a heat conductive filler, and the partition plate is divided into upper and lower inner tubes, wherein the upper inner tube is the first inner tube. The lower inner tube is a second inner tube, one end of which is aligned with one end of the outer tube, the lower tube wall of the first inner tube has a plurality of first holes, and the first inner tube and the outer tube have an air inlet Therefore, a second carrier gas is introduced to the cold outer tube and one end of the first inner tube. The second inner tube is located below the first inner tube and the upper inner wall of the second inner tube has a plurality of second holes. a filling portion between the first inner tube and the outer tube and between the second inner tube and the outer tube is filled with a thermal conductive material, and the length of the second inner tube corresponding to the filling portion is greater than the second corresponding to the second hole The length of the inner tube, and the tube outside the thermal conductive material has a second air inlet for introducing the first carrier gas. In addition, there is a distance between the two ends of the heater and the two ends of the outer officer, and the heater corresponds to a portion of the first inner tube and a portion of the second inner tube, thereby heating the portion of the tube. Therefore, the application of the invention can greatly improve the effective utilization rate of the heat handle provided by the heater, and reduce the production cost; the effect of mixing the carrier gas and the raw material gas can be increased, and the carbon fiber can be prevented from being generated in the pipe wall, thereby improving the yield. And easy to clean the reaction tube; can effectively utilize the overall heating of 1244883 energy, and generate a gas to cool at both ends of the reaction tube, and a good effect of heat reaction in the middle of the reaction tube. [Embodiment] The present invention provides a plurality of holes in a part of the inner wall of the inner tube of the vertical reaction tube structure, and a thermal conductive material is filled between the inner tube and the outer tube, thereby increasing the mixing effect of the carrier gas and the raw material gas; Prevent carbon fiber from forming on the inner wall of the inner tube; and improve heat transfer efficiency.
請參照第2圖和第3圖 不。同▼ ^ ....... _Please refer to Figure 2 and Figure 3 No. Same as ▼ ^ ....... _
較佳實施例之氣相成長碳纖維之反應裝置的結構示意 圖。第3圖為繪示本發明之較佳實施例之垂直式反應 官結構的俯視示意圖。本發明之氣相成長碳纖維的反應 裝置的主要部分為垂直式反應管結構1〇〇,垂直式反應管 結構100係由外管110、内管120所構成。内管12〇係位 於外管11〇中，且由隔板122分隔成上下内管12〇a和 120b，其中内管120a的上端對齊外管11〇的上端，内管 120a的上端具有進氣導管17〇，藉以通入原料氣體，此原 料氣體可為例如：石炭氫化物(例如：脂肪族或芳香族碳氫 化物）、反應催化劑（例如：Ferrocene; Fe(c5H5)2)和= (例如：氫氣），其中脂肪族碳氫化物為甲烧、乙貌、 乙炔、丙烧、液化石油氣、丁烧 ^ 丁烯、丁二烯等；苦夭 族碳氫化物為苯、曱苯、二甲苯等。 方曰 内管120a與外管11〇之鬥 之間的上端具有進氣口 不)’藉以經由管路32。通入載氣(例如：氫氣)來冷卻: 10 1248483 管uo和内管120a上端，止其中之密封材料受損。 又，〃内管120b係位於外管11〇中之内管12〇a的下方，、而 内管12〇a與内管12〇b之間具有距離（即隔板122)。此外， 加熱器' 15〇係安裝在外管11〇的周圍，其兩端與外管ιι〇 的兩端之間分別具有距離124和距離126，且加熱器BO 係對應於部分之内管120a和部分之内管12〇b，亦即加熱 器150僅對部分之外管11〇加熱，加熱器15〇的功率可為 例如：約10〜5 0kW。 本發明的特徵之一係在内管12〇a與外管11〇之間填 充熱導材料140，以及在内管12〇1)的上部與外管11〇之 間填充熱導材料140，而在熱導材料14〇下方之外管11〇 上具有進氣口（未標示），藉以經由管路33〇通入載氣（例 如·氫氣）。熱導材料14〇可為例如：陶瓷材料、金屬材 料、石英玻璃或其混合物。本發明的另一特徵係在内管 120a的下部管壁上設置複數個孔洞13〇a，以及内管12叽 的上部管壁設置複數個孔洞130b。熱導材料14〇於内管 120b之填充部分的長度可大於孔洞i3〇b所對應之内管 1 20b的長度。 當載氣經由管路330進入内管i2〇b與外管11〇之間 的區域後，向上透過孔洞i 3〇b進入内管i 2〇b中，此時， 由於固體熱導材料140的吸熱及傳熱速率遠大於習知之 引導氣體的特性，因此能將加熱器丨50所提供之熱能作最 有效的運用。另一方面，由管路320通入的冷載氣透過孔 洞130a進入内管120a中，此區域（如距離124所示）未受 11 1248483 到加熱器1 5 0加熱。在由孔洞1 3 Oa進入之冷载氣、由進 氣導管170通入之向下流的原料氣體、以及由孔洞13〇b 進入之熱載氣混合成反應氣體後，此反應氣體向下進入 反應區受熱分解而生成碳纖維。此時，向下流之反應氣 體與向上流之熱載氣形成反向（C〇unter-Flow)熱交換，因 而可更有效地進一步利用整體加熱能量，並可延長載氣升 溫時間，而提高其溫度。然後，所生成的碳纖維與殘餘反 應氣體向下流經冷卻區（如距離丨26所示；未受到加熱器 150加熱），藉以適當地冷卻碳纖維與殘餘反應氣體，接 著’碳纖維與殘餘反應氣體落入與内管l2〇b下端連接的 奴纖維收集系統400中。由於載氣係於室溫下在内管 120a和120b與外管11〇間逐漸加溫，而反應氣體係於 内管120a和120b中由上往下形成熱交換，加上前述 之冷卻區，故可有效降低碳纖維與殘餘反應氣體於碳纖 維收集系統400中的溫度。 綜上所述，本發明可呈現垂直式反應管結構100之兩 端冷卻而混合氣體在其中間受熱反應的效果。值得一提的 疋，孔洞1 30a和孔洞丨3〇b的設置可把載氣轉為向反應 裝置之内管的中心，以增加載氣與原料氣體（碳氫化合 物、反應催化劑和載氣）的混合效果，同時，由於載氣 分別自孔洞13〇a和孔洞13〇b喷出，可以有效地防止碳 纖維在内管管壁上生成。 另外’碳纖維收集系統400可連接至載氣回收系統 5 00 ’以回收殘餘混合氣體中的載氣。回收的載氣經由管 12 1248483 =510進入管路3〇2’與由載氣源、3〇〇所提供的載氣混 =，然後分成三部分，經由管路31〇、管路32〇和管路33〇， ^別進入混合器210和垂直式反應管結構1〇〇。進入混合 益210的載氣與由原料及催化劑氣體源所提供的氣 體混合成反應氣體，其中此反應氣體可先經預熱器16〇 預熱後再進入内管12〇a。 又，垂直式反應管結構1〇〇的内外管可為如第3圖所 示之圓管形狀，其材質可為氧減、碳㈣、石英、富紹 =柱石（mullite)和氮化石夕等，然而，其形狀亦可為如方形 · 管等其他形狀，其材質亦可為其他材質，故本發明並不在 此限。 又，請參照第4圖，其為繪示本發明所填充之各種形 狀熱導材料的示意圖。 以下比較本發明之製程實施例和習知對照例來說明 本發明： 支叠明之製裎實施例 於如第2圖中所示之氣相成長碳纖維反應裝置中，以 _ 下列條件來製作氣相成長碳纖維。 首先，由原料及催化劑氣體源200輸送原料氣體至混 合器210與部分載氣混合均勻後，輸送原料氣體與載氣之 反應氣體至預熱器160預熱至3〇〇t。接著，預熱後之反 應氣體由進氣導管170導入反應爐體進行反應。同時剩餘 載氣分別由管路320、管路33〇輸送至内管12(^和12〇b 與外管no @ ’内管與外管110間填充熱導材料14〇，加 13 1248483 熱器150於管外加熱反應爐體γ*卜管11〇)與熱導材料 wo,载氣經由熱導材料140加熱後，由孔洞l3〇a、孔洞 13〇b噴出迗入内官12〇&和12〇b。所得產物於碳纖維收集 系統400中收集，剩餘廢氣由載氣回收系統5〇〇回收循環 使用。 衣 本製程實施例之垂直式反應管結構1〇〇的規格與操 作條件為： ' (1) 内管120 :内徑20 cm、外徑24 cm、長度2〇〇公 分之石英管。 (2) 外管110 ·•内徑30 cm、外徑34 cm、長度200公 分之石英管。 (3) 孔洞 130a : 位置·由反應管上方距離3 5公分處開始，向下J 5 公分之範圍，孔徑·直桎2公釐小孔，每小孔距離1公分。 (4) 孔洞 130b : 位置：由反應管上方距離51公分處開始，向下3〇 公分之範圍；孔徑：直桎2公釐小孔，每小孔距離1公分 (5) 隔板122 :内徑20 cm、外徑30 cm、厚1 cm之石 英圓板；位置：由反應管上方距離5〇〜5 1公分處。 (6) 熱導材料140:石英材質，如第4圖所示之填充料 種類-a (内徑〇·8公分，外徑1.0公分，長度ι·2公分）。 (6) 加熱器150的控制溫度：1200。〇。 (7) 原料氣體供給系統：反應原料組成：Xylene : 96 wt %、Ferrocene : 4 wt% ;反應原料流量：6〇 mi/min (液 14 1248483 態：25°C ' —大氣壓下），氣化後導入反應系統。 (8) 載氣種類：氫氣；載氣流量：20 L/min (由進氣導 管 170 導入）、30 L/min (由孔洞 130a 導入）、1〇〇 L/min (由孔洞130b導入） 反應時間：兩小時 (9) 產物：2.52 Kg (收率約45%，清理管壁時，管壁 上無附著），碳纖維平均直徑為200 nm。 請參照第5圖，其為本發明之製程實施例所製成之產 物的SEM(JEOL JSM63 60)圖。由第5圖可知，本製程實 施例之產物的純度相當高。 對照例 於如第1A圖所示之裝置中，原料氣體與部分載氣由 進氣導管10導入反應爐管中進行反應，同時剩餘載氣由 進氣口 20導入反應爐管中反應，加熱器50並於管外加 熱，而所得產物由收集槽60收集。 本習知對照例所使用之規格與操作條件為： (1) 反應管40:内徑20 cm、外徑24 cm、長度2〇〇 公分之石英管， (2) 加熱器50的控制溫度·· i2〇〇°C。 (3) 反應原料組成：Xyiene : 96 wt%、Ferrocene : 4 wt % ;反應原料流量·· 60 ml/min (液態·· 25°C、一大氣壓 下），氣化後導入反應系統。 (4) 載氣種類：氫氣；載氣流量：2〇 L/min (由進氣導 官10導入）、130 L/min (由進氣口 20導入）。 15 1248483 (5)反應時間：2小時 \ _ ⑹產物：0.84Kg (收率：約15%、反應爐清理時， 管壁上附者許多產物），碳纖維平均直徑则腿。 請參照第6圖，其為習知對照例所製成之產物的 SEM(JEOL JSM6360)圖。由第6圖可知，習知對照例之產 物中的非纖維狀雜質相當多。 因此，由上述本發明較佳實施例和製程實施例可知， 應用本發明的優點為：可大幅地提升加熱器所提供之教 能的有效利用率；可增加載氣與原料氣體混合之效果，# 並防止碳纖維在管壁生成’且易於清理反應管；可獲得 高純度的產物；可有效地利用整體加熱能量，並產生氣 體在反應官之兩端冷卻，而在反應管之中間受熱反應 的良好效果。 μ ~ 雖然本發明已以一較佳實施例揭露如上，然其並非用 以限定本發明，任何熟習此技藝者，在不脫離本發明之精 神和範圍π ’當可作各種之更動與潤冑，因Λ本發明之保 護範圍當視後附之申請專利冑圍所界定者為$。 鲁 【圖式簡單說明】 第1Α圖和第1 β圖為緣示習知之氣相成長碳纖維之 反應裝置的結構示意圖。 第2圖為緣示本發明之較佳實施例之氣相成長碳纖 維的反應裝置之結構示意圖。 第3目為緣不本發明之較佳實施例之垂直式反應管 16 1248483 結構的俯視示意圖。 第4圖為繪示本發明所填充之各種形狀熱導材料的 示意圖。 第5圖為本發明之製程實施例所製成之產物的 SEM(JEOL JSM6360)圖。 第6圖為習知對照例所製成之產物的SEM(JEOL JSM6360)圖。 【元件代表符號簡單說明】 10 ： 進氣導管 20 ：： 進氣口 30 ： 内管 40 :外管 50 ： 加熱器 60 :收集槽 100 :垂直式反應管結構 110 :外管 120 ： 内管 120a 、 120b :内管 122 ： 隔板 124 、12 6 :距離 130a 、130b ：孑L 洞 140 :熱導材料 150 ： 加熱器 160 :預熱器 170 ： 進氣導管 200 :原料及催化劑 氣體源 210 :混合器 300 :載氣源 302 、310 :管路 320 、330 :管路 400 :碳纖維收集系 統 500 :載氣回收系統 510 :管路 17A schematic view of the structure of a reaction apparatus for vapor-grown carbon fibers of a preferred embodiment. Figure 3 is a top plan view showing the vertical reaction structure of the preferred embodiment of the present invention. The main part of the reaction apparatus for vapor-phase-growth carbon fibers of the present invention is a vertical reaction tube structure 1 , and the vertical reaction tube structure 100 is composed of an outer tube 110 and an inner tube 120. The inner tube 12 is located in the outer tube 11〇, and is partitioned by the partition plate 122 into upper and lower inner tubes 12〇a and 120b, wherein the upper end of the inner tube 120a is aligned with the upper end of the outer tube 11〇, and the upper end of the inner tube 120a has intake air. a conduit 17 through which a feed gas is introduced, which may be, for example, a charcoal hydride (eg, an aliphatic or aromatic hydrocarbon), a reaction catalyst (eg, Ferrocene; Fe(c5H5)2), and = (eg : Hydrogen), wherein the aliphatic hydrocarbons are methyl ketone, ethyl acetate, acetylene, propane burning, liquefied petroleum gas, butadiene, butadiene, butadiene, etc.; the tartary hydrocarbons are benzene, benzene, and Toluene, etc. The upper end between the inner tube 120a and the outer tube 11's bucket has an air inlet port. Cooling with a carrier gas (eg hydrogen): 10 1248483 Tube uo and upper end of inner tube 120a, the sealing material is damaged. Further, the inner tube 120b is located below the inner tube 12A in the outer tube 11A, and has a distance between the inner tube 12a and the inner tube 12b (i.e., the partition 122). In addition, the heater '15〇 is installed around the outer tube 11〇, and has a distance 124 and a distance 126 between the two ends and the two ends of the outer tube ιι, respectively, and the heater BO corresponds to a part of the inner tube 120a and The inner tube 12〇b, that is, the heater 150 is only heated to a portion of the outer tube 11〇, and the power of the heater 15〇 can be, for example, about 10 to 50 kW. One of the features of the present invention is that the thermal conductive material 140 is filled between the inner tube 12A and the outer tube 11?, and the thermal conductive material 140 is filled between the upper portion of the inner tube 12?) and the outer tube 11? Outside the heat conductive material 14〇, the tube 11 has an air inlet (not shown) through which a carrier gas (for example, hydrogen gas) is introduced. The thermally conductive material 14A can be, for example, a ceramic material, a metal material, quartz glass, or a mixture thereof. Another feature of the present invention is that a plurality of holes 13a are provided in the lower tube wall of the inner tube 120a, and a plurality of holes 130b are provided in the upper tube wall of the inner tube 12''. The length of the filling portion of the heat conductive material 14 to the inner tube 120b may be greater than the length of the inner tube 1 20b corresponding to the hole i3〇b. When the carrier gas enters the region between the inner tube i2〇b and the outer tube 11〇 via the pipeline 330, it passes through the hole i 3〇b into the inner tube i 2〇b, at this time, due to the solid thermal conductive material 140 The heat absorption and heat transfer rate is much greater than the characteristics of the conventional guiding gas, so that the heat energy provided by the heater 丨50 can be used most effectively. On the other hand, the cold carrier gas passing through the line 320 passes through the hole 130a into the inner tube 120a, and this area (as indicated by the distance 124) is not heated by the 11 1248483 to the heater 150. After the cold carrier gas entering through the hole 1 3 Oa, the downward flowing raw material gas introduced by the intake pipe 170, and the hot carrier gas entering through the hole 13〇b are mixed into a reaction gas, the reaction gas enters the reaction downward. The zone is thermally decomposed to form carbon fibers. At this time, the downward flowing reaction gas forms a reverse (C〇unter-Flow) heat exchange with the upward flowing hot carrier gas, so that the overall heating energy can be further utilized more effectively, and the carrier gas heating time can be prolonged, and the carrier gas can be increased. temperature. Then, the generated carbon fiber and the residual reaction gas flow downward through the cooling zone (as indicated by the distance 丨26; not heated by the heater 150), thereby appropriately cooling the carbon fiber and the residual reaction gas, and then the 'carbon fiber and the residual reaction gas fall into In the slave fiber collection system 400 connected to the lower end of the inner tube l2〇b. Since the carrier gas is gradually warmed between the inner tubes 120a and 120b and the outer tube 11 at room temperature, the reaction gas system forms heat exchange from the top to the bottom in the inner tubes 120a and 120b, plus the aforementioned cooling zone, Therefore, the temperature of the carbon fiber and the residual reaction gas in the carbon fiber collecting system 400 can be effectively reduced. In summary, the present invention can exhibit the effect that both ends of the vertical reaction tube structure 100 are cooled and the mixed gas is thermally reacted therebetween. It is worth mentioning that the arrangement of the hole 1 30a and the hole 丨3〇b can turn the carrier gas into the center of the inner tube of the reaction device to increase the carrier gas and the raw material gas (hydrocarbon, reaction catalyst and carrier gas). At the same time, since the carrier gas is ejected from the holes 13〇a and the holes 13〇b, respectively, the carbon fibers can be effectively prevented from being generated on the inner tube wall. Further, the carbon fiber collection system 400 can be connected to a carrier gas recovery system 500' to recover the carrier gas in the residual mixed gas. The recovered carrier gas is mixed into the pipeline 3〇2' via the pipe 12 1248483 = 510 and mixed with the carrier gas supplied by the carrier gas source, and then divided into three parts, via the pipeline 31〇, the pipeline 32〇 and The line 33 is not in the mixer 210 and the vertical reaction tube structure 1〇〇. The carrier gas entering the mixed benefit 210 is mixed with the gas supplied from the raw material and the catalyst gas source to form a reaction gas, wherein the reaction gas can be preheated by the preheater 16 后 before entering the inner tube 12〇a. Further, the inner and outer tubes of the vertical reaction tube structure may be in the shape of a circular tube as shown in Fig. 3, and the material thereof may be oxygen reduction, carbon (tetra), quartz, fusau = mullite, and nitrite. However, the shape may be other shapes such as a square tube or the like, and the material thereof may be other materials, so the present invention is not limited thereto. Further, please refer to Fig. 4, which is a schematic view showing various shapes of thermal conductive materials filled in the present invention. The following is a comparison of the process examples of the present invention and the conventional comparative examples to illustrate the present invention: In the vapor-phase growth carbon fiber reaction apparatus shown in Fig. 2, the gas phase is produced in the following conditions: Growing carbon fiber. First, the raw material gas is supplied from the raw material and the catalyst gas source 200 until the mixer 210 is uniformly mixed with the partial carrier gas, and then the reaction gas of the raw material gas and the carrier gas is supplied to the preheater 160 to be preheated to 3 Torr. Then, the preheated reaction gas is introduced into the reaction furnace body by the intake pipe 170 to carry out a reaction. At the same time, the remaining carrier gas is respectively transported from the pipeline 320 and the pipeline 33 to the inner pipe 12 (^ and 12〇b and the outer pipe no @ 'the inner pipe and the outer pipe 110 are filled with the heat conductive material 14〇, and the 13 1248483 heat exchanger is added. 150 is heated outside the tube to heat the reaction furnace body γ*b tube 11〇) and the thermal conductive material wo, after the carrier gas is heated by the heat conductive material 140, the hole 133〇a, the hole 13〇b is ejected into the inner 12〇& 12〇b. The resulting product is collected in a carbon fiber collection system 400, and the remaining exhaust gas is recycled from the carrier gas recovery system. The specifications and operating conditions of the vertical reaction tube structure of the garment process example are as follows: ' (1) Inner tube 120: a quartz tube having an inner diameter of 20 cm, an outer diameter of 24 cm, and a length of 2 cm. (2) Outer tube 110 • A quartz tube with an inner diameter of 30 cm, an outer diameter of 34 cm and a length of 200 cm. (3) Hole 130a: Position · Starting from the distance of 3 5 cm above the reaction tube, down to the range of 5 cm, the diameter of the hole is 2 mm, and the distance per hole is 1 cm. (4) Hole 130b: Position: starting from the distance of 51 cm above the reaction tube, down to 3 cm; aperture: straight 2 cm, each hole 1 cm (5) Separator 122: inside Quartz disc with a diameter of 20 cm, an outer diameter of 30 cm and a thickness of 1 cm; position: 5 〇 to 5 1 cm above the reaction tube. (6) Thermal conductive material 140: Quartz material, as shown in Fig. 4, the type of filler - a (inner diameter 〇 · 8 cm, outer diameter 1.0 cm, length ι · 2 cm). (6) Control temperature of heater 150: 1200. Hey. (7) Raw material gas supply system: reaction raw material composition: Xylene: 96 wt %, Ferrocene: 4 wt%; reaction raw material flow rate: 6〇mi/min (liquid 14 1248483 state: 25 ° C '-atmospheric pressure), gasification After the introduction into the reaction system. (8) Carrier gas type: hydrogen; carrier gas flow rate: 20 L/min (introduced by intake conduit 170), 30 L/min (introduced by hole 130a), 1 〇〇L/min (introduced by hole 130b) Time: two hours (9) Product: 2.52 Kg (yield about 45%, no adhesion on the tube wall when cleaning the tube wall), the average diameter of the carbon fiber is 200 nm. Please refer to Fig. 5, which is a SEM (JEOL JSM63 60) diagram of the product produced by the process examples of the present invention. As can be seen from Figure 5, the purity of the product of this process example is quite high. In the apparatus shown in FIG. 1A, the raw material gas and a part of the carrier gas are introduced into the reaction tube through the intake duct 10 for reaction, and the remaining carrier gas is introduced into the reaction tube through the inlet 20 to react. 50 and heated outside the tube, and the resulting product is collected by collection tank 60. The specifications and operating conditions used in the comparative examples are as follows: (1) Reaction tube 40: a quartz tube having an inner diameter of 20 cm, an outer diameter of 24 cm, a length of 2 cm, and (2) a control temperature of the heater 50. · i2〇〇°C. (3) Reaction raw material composition: Xyiene: 96 wt%, Ferrocene: 4 wt%; reaction raw material flow rate · 60 ml/min (liquid · · 25 ° C, at atmospheric pressure), and then introduced into the reaction system after gasification. (4) Type of carrier gas: hydrogen; carrier gas flow rate: 2 〇 L/min (introduced by intake guide 10), 130 L/min (introduced by air inlet 20). 15 1248483 (5) Reaction time: 2 hours \ _ (6) Product: 0.84Kg (yield: about 15%, when the reactor is cleaned, many products are attached to the tube wall), and the average diameter of the carbon fiber is the leg. Please refer to Fig. 6, which is a SEM (JEOL JSM6360) diagram of a product prepared by a conventional comparative example. As is apparent from Fig. 6, the non-fibrous impurities in the products of the conventional comparative examples are quite large. Therefore, it can be seen from the above preferred embodiments and process embodiments of the present invention that the advantages of applying the present invention are that the effective utilization rate of the teaching energy provided by the heater can be greatly improved; and the effect of mixing the carrier gas and the raw material gas can be increased. # and prevent carbon fiber from forming on the tube wall and easy to clean the reaction tube; high purity products can be obtained; the overall heating energy can be effectively utilized, and the gas is cooled at both ends of the reaction column, and is heated in the middle of the reaction tube. Good results. Although the present invention has been disclosed in a preferred embodiment as above, it is not intended to limit the invention, and any person skilled in the art can make various changes and simplifications without departing from the spirit and scope of the invention. As the scope of protection of the present invention is defined as $, the scope defined in the attached patent application. Lu [Simplified Schematic Description] The first diagram and the first beta diagram are schematic diagrams showing the structure of a conventional gas phase growth carbon fiber reaction apparatus. Fig. 2 is a schematic view showing the structure of a reaction apparatus for vapor-grown carbon fibers according to a preferred embodiment of the present invention. The third item is a schematic plan view of the structure of the vertical reaction tube 16 1248483 which is not a preferred embodiment of the present invention. Fig. 4 is a schematic view showing various shapes of thermally conductive materials filled in the present invention. Figure 5 is a SEM (JEOL JSM6360) diagram of the product produced by the process examples of the present invention. Fig. 6 is a SEM (JEOL JSM6360) diagram of a product prepared by a conventional comparative example. [Simplified description of component symbol] 10 : Intake conduit 20 :: Inlet 30 : Inner tube 40 : Outer tube 50 : Heater 60 : Collection tank 100 : Vertical reaction tube structure 110 : Outer tube 120 : Inner tube 120a 120b: inner tube 122: partitions 124, 12 6 : distance 130a , 130b : 孑 L hole 140 : thermal conductive material 150 : heater 160 : preheater 170 : intake duct 200 : raw material and catalyst gas source 210 : Mixer 300: carrier gas source 302, 310: line 320, 330: line 400: carbon fiber collection system 500: carrier gas recovery system 510: line 17