TWI362430B - Apparatus and method for manufacturing a carbon nanotube - Google Patents

Description

100 years. July 15th, nuclear replacement page 13624, 30 r ·» VI. Description of the invention: [Technical field of invention] [0001] The present invention relates to a device for preparing a carbon nanotube and a preparation method thereof. [Former Technology Street]

[0002] The carbon nanotube is a tubular graphite discovered by the researcher Iijima in 1991, see "Helical Microtubules of Graphitic Carbon", S Iijima, Nature, Vol. 354, P. 56 (1991) . Due to its excellent electrical conductivity and unidirectional heat conduction, it has attracted widespread attention to carbon nanotubes. The preparation of nanocarbon tubes has also been the focus of scientific research. [0003] The method for preparing a carbon nanotube is an arc discharge method (Arc Di scharge), a laser ablation method, a chemical vapor deposition method (CVD), or the like, wherein the CVD method grows nanometer. The carbon tube has the advantages of simple equipment, low cost and large size. [0004] A typical CVD growth carbon nanotube device includes a high temperature heating furnace, a quartz furnace tube, a boat disposed in the quartz furnace tube, and a The substrate inside the boat. When preparing the carbon nanotubes, a catalyst layer is first deposited on the substrate, then the quartz furnace tube is heated, a carbon source gas is introduced, and the carbon source gas is reacted on the catalyst layer at a high temperature to grow a carbon nanotube. The device grows carbon tubes by means of high temperature thermal decomposition of carbon source gas, and the reaction temperature ranges from 500 to 1 000 ° C. Due to the high reactivity of the carbon nanotubes at high temperatures, the carbon tubes are easily reacted with air, so they grow up. After the reaction, the carbon tube cannot be taken out directly under high temperature, and must be taken out until the temperature in the high temperature furnace drops below 300 °C. Therefore, during the entire carbon tube preparation process, there are 094127472 Form No. A0101 Page 3 / Total 16 Page 1003256786-0 1362430 [0005] [0007] [0008] [0010] [0011] [0012] 0013] [0014] 100 years. July 15th, the revised alternative effect is shorter, and the time for heating and cooling is longer, accounting for more than 80% of the whole process time, which greatly reduces the carbon nanotubes. The preparation efficiency is therefore particularly important to improve the preparation efficiency of the carbon nanotubes. SUMMARY OF THE INVENTION Hereinafter, a carbon nanotube preparation apparatus and a preparation method for improving the production efficiency of a carbon nanotube will be described by way of embodiments. The carbon nanotube preparation apparatus includes a reaction chamber modified to provide a cooling device in the reaction chamber or at the outer surface of the reaction chamber. The cooling device includes a cavity disposed at an inner surface of the reaction chamber, the chamber containing a cooling working substance. The cooling device includes a plurality of cooling tubes disposed in the reaction chamber, and the cooling tube contains a cooling working substance. The cooling device includes at least one cooling tube disposed on an outer surface of the reaction chamber, the cooling tube containing a cooling working substance. The cooled working substance flows in the cooling device. The method for preparing a carbon nanotube is opposite to the direction of gas flow in the reaction chamber, and comprises the steps of: providing a carbon nanotube preparation device, wherein the preparation device of the carbon nanotube comprises a reaction chamber, a substrate, the improvement is that a cooling device is disposed in the reaction chamber or at the outer surface of the reaction chamber; a catalyst layer is deposited on the substrate;

094127472 Form No. A0101 1003256786-0 13624, 30 [0016] [0017] 100 years. July 15th, according to the replacement page, the reaction chamber is heated to the reaction temperature to grow the carbon nanotubes; The working substance was cooled, and the reaction chamber was cooled to below 300 ° C to take out the carbon nanotubes. The cooling device includes a cavity disposed at an inner surface of the reaction chamber. [0018] The cooling device includes a plurality of cooling tubes disposed in the reaction chamber, and the cooling tube includes a cooling working substance.

[0019] The cooling device includes at least one cooling tube disposed on an outer surface of the reaction chamber, and the cooling tube includes a cooling working substance. [0020] Compared with the prior art, the apparatus used in the preparation device and the preparation method of the carbon nanotube includes a cooling device, and the cooling device can pass a cooling working substance, which can rapidly cool the reaction chamber and the gas therein, The cooling time in the reaction chamber from the reaction temperature to the temperature at which the carbon nanotubes can be taken out is reduced, and the preparation efficiency is improved. [0021] The cooling working substance can enhance the cooling effect when flowing, and further improve the preparation efficiency.

[0022] The flow direction of the cooling working substance is opposite to the flow direction of the gas in the reaction chamber. Since the gas entering the reaction chamber has a higher temperature, the cooling working substance forms a countercurrent with the gas in the reaction chamber, and the cooling effect is better. . [Embodiment] [0023] Hereinafter, a carbon nanotube preparation apparatus and a preparation method will be described with reference to the drawings: [0024] Referring to the first diagram and the second diagram, the carbon nanotube preparation apparatus 100 of the first embodiment includes a Reaction chamber 10, a boat 30, 094127472 disposed in the reaction chamber Form No. A0101 Page 5 / Total 16 pages 1003256786-0 1362430 1001⁄2 07月ίί 曰 A substrate 40' disposed in the boat - for heating reaction The heating portion 20 of the cavity and a cooling device. The reaction chamber 10 may be a sealable cavity formed of a material having stable chemical properties and high temperature resistance. The material is preferably quartz, and a gas inlet 101 and a gas outlet 1〇2 are respectively disposed at two ends thereof; the substrate 40 may be a porous second The substrate or a gas-shield substrate may be any material which has a phenomenon of no chemical reaction or atomic penetration of the catalyst in the south temperature and the subsequent step, and the surface is required to be clean without destroying the subsequent reaction conditions. The heating part 2〇

It is disposed outside the reaction chamber 10 near the reaction chamber 10, which can heat the reaction chamber. Preferably, the heating portion 20 is closely surrounding the reaction chamber 1 to achieve a uniform heating effect, so as to be disposed corresponding to the boat 30. A heat-conducting material layer 80 is disposed between the heating portion 20 and the reaction chamber 1〇 to achieve a better heating effect. The heat-conducting material may be a heat-dissipating paste, a heat-conductive gasket, or the like, and has a high heat transfer coefficient, and It can be in close contact with the adding portion 20 and the reaction chamber 1 ,, which can increase the thermal conductivity and provide more uniform heating; the cooling device comprises a casing disposed in the reaction chamber 10 and a casing wall 50 of the reaction chamber 10 The cavity 51 is preferably made of the same material as the reaction chamber. The cavity 51 is provided with an inlet 5〇1 and an outlet 5〇2, and the inlet 501 can inject a cooling working substance into the cavity. The cooling working substance is preferably water, methanol, ethanol, acetone, hexane, liquid ammonia, liquid nitrogen or a mixture thereof, and preferably the cooling working substance is in a flowing state, such as connecting the inlet 5〇1 and the outlet 502 to the cooling working substance circulation. System, more Preferably, the inlet 501 provided to adjust the position 502 of the cooling working substance flow direction of the reaction chamber 10 opposite to the gas flow, counterflow to enhance the cooling effect. In order to avoid the cooling capacity of the cooling working substance due to the insufficient outer diameter of the tube wall 50 due to the insufficient outer diameter of the tube wall 51 and the outer diameter being too small, it is preferable to make the outer diameter of the tube wall 50 and the inner diameter of the reaction chamber 10 ratio 〇. 5-0. 8 094127472 Form No. A0101 Page 6 of 16 Page 1003256786-0 1362430 · · . 100 years. July 15th revised for 4 pages. As the density of the gas becomes larger, it will sink in the reaction chamber. 'The hot gas rises', so the hot gas at the top of the reaction chamber is more. 'To improve the cooling efficiency, the tube wall 5〇 can be placed near the bottom of the reaction chamber. 'There is a larger space for the cavity near the top of the reaction chamber to accommodate more cooling work material' for better cooling.

[0025] Referring to the third and fourth figures, the carbon nanotube preparation apparatus 200 of the second embodiment is different from the carbon nanotube preparation apparatus 100 of the first embodiment in that the cooling apparatus includes a reaction set. A plurality of cooling tubes 60 in the chamber 10. An inlet 6〇1 and an outlet 602m′ are respectively disposed at two ends of the cooling pipe, and the cooling working substance is injected into the cooling pipe through the inlet 6〇1, and preferably, the cooling work substance is in a flowing state, and more preferably The direction of flow of the cooling working substance is opposite to the direction of gas flow in the reaction chamber 1〇. In this embodiment, since a plurality of cooling tubes are used, the cooling working substance has a larger contact area with the gas in the reaction chamber, which is more convenient for cooling. The ratio of the outer diameter of the outer diameter of the cooling tube 60 to the inner diameter of the reaction chamber 10 is between -01 and 1.25. More preferably, the distribution density of the cooling tube at the top of the reaction chamber 1 is greater than the distribution density of the cooling tube at the bottom of the reaction chamber. [0026] Please refer to the fifth figure, the carbon nanotube preparation device 300 and the third embodiment The carbon nanotube preparation apparatus 100 of one embodiment differs in that the cooling apparatus includes at least one cooling tube 70 disposed at an outer surface of the reaction chamber 10. The cooling tube 70 is wound around the outer surface of the reaction chamber 10 and is immersed in the heat conductive material layer 80. Both ends thereof are provided with an inlet 701 and an outlet 702'. The inlet 701 can pass a cooling working substance into the cooling tube. Preferably, The cooling working substance is in a flowing state, and more preferably the cooling working substance 094127472 Form No. 1010101 Page 7 / Total 16 pages 1003256786-0 1362430 100 years. July 15th Shuttle is replacing the flow direction of the page and the gas in the reaction chamber 1 0 The flow direction is reversed. The cooling pipe 70 in the present embodiment is located between the heating portion 20 and the reaction chamber 10. In order to achieve a balance between heating efficiency and cooling efficiency, in addition to using a better heat conductive material, it is preferable to make the cooling pipe 70 between two turns. 5-2之间。 The ratio of the distance between the 0. 5-2.

[0027] The carbon nanotube preparation device in the above embodiments includes a cooling device, and after the carbon nanotube growth reaction is completed, a cooling working substance can be introduced into the cooling device to rapidly cool the reaction chamber and the gas therein. To improve the preparation efficiency of the carbon nanotubes; in order to further accelerate the cooling rate, the cooling device can also be connected to the cooling working material circulation system; more preferably, the cooling working material flows in the opposite direction to the gas flow direction in the reaction chamber, and the cooling effect is further improved. good. [0028] Please refer to the sixth figure, taking the carbon nanotube preparation device 100 of the above-mentioned first embodiment as an example, the present invention also provides a method for preparing a carbon nanotube, which comprises the following steps: [0029] Step 1, provide A carbon nanotube preparation apparatus 100. [0030] Step 2, depositing a catalyst layer on the substrate 40, the catalyst is generally a transition metal Fe ' Co ' Ni or Fe ' Co ' Ni oxide, or contains Fe,

The alloy of Co and Ni has a deposition thickness of l~10 nm. [0031] Step 3, heating the reaction chamber to a predetermined temperature, which is related to the carbon source gas used to grow the carbon nanotubes, generally 500-1 00 (TC. [0032] Step 4, introducing a carbon source gas [0030] Step 5, stop heating, pass cooling working substance into the cavity, cool 094127472 Form No. A0101 Page 8 / Total 16 Page 1003256786-0 1362430 Pressed on July 15, 100 The sheet reaction chamber is replaced below 300 ° C to take out the carbon nanotubes. The cooling working substance has a large heat absorption capacity, preferably one of water, methanol, ethanol, acetone, hexane, liquid helium, liquid nitrogen or The mixture can be replaced with a new cooling working substance when the cooling working material absorbs a certain amount of heat and loses the cooling capacity. More preferably, the cooling device can be connected to the cooling working material circulation system. Since the gas entering the reaction chamber first has a higher temperature More preferably, the cooling working substance flows in from the gas outlet side and flows out from the gas inlet side, and the cooling working substance forms a countercurrent with the gas, and the cooling effect is further improved.

[0034] In the first step of the method for preparing a carbon nanotube, the carbon nanotube preparation device of the second embodiment or the third embodiment may be used, and the operation steps are similar to the preparation method of the above carbon nanotube. [0035] Compared with the prior art, the apparatus used in the preparation device and the preparation method of the carbon nanotube includes a cooling device, and the cooling working substance can be introduced into the cooling device to rapidly cool the reaction chamber and the gas therein, thereby saving Cooling time to improve preparation efficiency. The cooling working substance can enhance the cooling effect when flowing, and further improve the preparation efficiency.

[0036] In summary, the present invention has indeed met the requirements of the invention patent, and the patent application is filed according to law. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application of the present invention. Equivalent modifications or variations made by persons skilled in the art in light of the spirit of the invention are intended to be included within the scope of the following claims. BRIEF DESCRIPTION OF THE DRAWINGS [0037] The first drawing is a schematic cross-sectional view of a carbon nanotube preparation apparatus according to a first embodiment of the present invention, 094127472 Form No. A0101 Page 9 of 16 1003256786-0 1362430 100.07 Ϊ5: Repair replacement page [0038] The second diagram is a cross-sectional view of the above-mentioned carbon nanotube preparation device along the ΙΙ-ΙΙ; [0039] The third diagram is a schematic cross-sectional view of the second embodiment of the present invention [0040] FIG. 4 is a cross-sectional view of the above-described carbon nanotube preparation apparatus taken along line IV-IV; [0041] FIG. 5 is a schematic structural view of a carbon nanotube preparation apparatus of a third embodiment of the present invention; [0042] It is a flow chart of a method for preparing a carbon nanotube. [Main component symbol description]

[0043] Reaction chamber: 10 [0044] Heating portion: 2 0 [0045] Carrier boat: 30 [0046] Substrate: 40 [0047] Tube wall: 50 [0048] Cooling tube: 60 [0049] Cooling tube: 70 [ 0050] Thermally conductive material layer: 80 [0051] Gas inlet: 101 [0052] Gas outlet: 102 [0053] Entrance: 501, 601, 701 [0054] Exit: 502, 602, 702 Form No. Α 0101 094127472 Page 10 / Total 16 pages 1003256786-0

Claims (1)

1362430 Shuttle page replacement page on July 15, 100 VII. Patent application scope: 1. A device for preparing a carbon nanotube, comprising a reaction chamber for accommodating a reaction gas, wherein the improvement is that a cooling device is disposed in the reaction chamber or at an outer surface of the reaction chamber, wherein the cooling device The tubes are distributed at the top and bottom of the reaction chamber, and the distribution density of the cooling tubes at the top of the reaction chamber is greater than the distribution density of the cooling tubes at the bottom of the reaction chamber. 2. The apparatus for preparing a carbon nanotube according to claim 1, wherein the cooling device comprises a wall disposed in the reaction chamber, the wall forming a cavity with the reaction chamber, the chamber The body contains cooling work substances. 3. The ratio of the outer diameter of the tube wall to the inner diameter of the reaction chamber is in the range of 0. 5-0. Σ 4 as in the patent application scope. The preparation device of the carbon nanotubes is disposed near the bottom of the reaction chamber. 5. The apparatus for preparing a carbon nanotube according to claim 1, wherein the cooling device comprises a plurality of cooling tubes disposed in the reaction chamber, the plurality of cooling tubes containing a cooling working substance. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。. 7. The apparatus for preparing a carbon nanotube according to claim 1, wherein the cooling device comprises at least one cooling pipe disposed at an outer surface of the reaction chamber, the cooling tube containing a cooling working substance. 8. The apparatus for preparing a carbon nanotube according to claim 7, wherein the cooling tube surrounds the surface of the reaction chamber. 9. The apparatus for preparing a carbon nanotube according to claim 8, wherein a ratio of a distance between two adjacent turns of the cooling pipe to a diameter of the cooling pipe is wherein 094127472 form number A0101 page 11 / Total 16 pages 1003256786-0 1362430 100 years. 07. Month 5 days to replace the replacement hundred, --- 0. 5-2. · ' * - * ίο . 11 . 12 . 13 . 14 . 15 . The apparatus for preparing a carbon nanotube according to the second aspect of the invention, or the fifth or the seventh aspect, wherein the cooling working substance Including water, methanol, ethanol, propylene, hexane, liquid gas, liquid nitrogen or a mixture thereof. A method for preparing a carbon nanotube, comprising the steps of: providing a carbon nanotube preparation device, the carbon nanotube preparation device comprising a reaction chamber, a substrate, wherein the reaction chamber or the outer surface of the reaction chamber a cooling device is disposed; a catalyst layer is deposited on the substrate; the reaction chamber is heated to a predetermined temperature; a carbon source gas is introduced into the reaction chamber to grow a carbon nanotube; and the cooling working substance is introduced into the cooling device to cool The reaction chamber is below 300 ° C to take out the carbon nanotubes. The method for preparing a carbon nanotube according to claim 11, wherein the cooling device comprises a wall disposed in the reaction chamber, the tube wall and the reaction chamber forming a cavity in the cavity Contains cooling work substances. The method for preparing a carbon nanotube according to claim 11, wherein the cooling device comprises a plurality of cooling tubes disposed in the reaction chamber, the cooling tube containing a cooling working substance. The method for preparing a carbon nanotube according to claim 13, wherein the cooling working substance flows in the cooling tube. The method for preparing a carbon nanotube according to claim 11, wherein the cooling device comprises at least one cooling pipe disposed at an outer surface of the reaction chamber, the cooling tube containing a cooling working substance. 094127472 Form No. A0101 Page 12 of 16 1003256786-0