[go: up one dir, main page]

WO2006088322A1 - Systeme de fabrication industrielle de nanotubes de carbone et procede de fabrication industrielle - Google Patents

Systeme de fabrication industrielle de nanotubes de carbone et procede de fabrication industrielle Download PDF

Info

Publication number
WO2006088322A1
WO2006088322A1 PCT/KR2006/000541 KR2006000541W WO2006088322A1 WO 2006088322 A1 WO2006088322 A1 WO 2006088322A1 KR 2006000541 W KR2006000541 W KR 2006000541W WO 2006088322 A1 WO2006088322 A1 WO 2006088322A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
reaction chamber
specific gravity
different
region
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2006/000541
Other languages
English (en)
Inventor
Yong Hoon Park
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CNT Co Ltd
Original Assignee
CNT Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by CNT Co Ltd filed Critical CNT Co Ltd
Publication of WO2006088322A1 publication Critical patent/WO2006088322A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts

Definitions

  • the present invention relates to a mass production system for synthesized carbon nanotubes, and a mass production method thereof using the same. More particularly, the present invention relates to a mass production system for synthesized carbon nanotubes using a vapor synthesis method, and a mass production method thereof using the same.
  • the present invention relates to a mass production system for synthesized carbon nanotubes, and a mass production method thereof using the same. More particularly, the present invention relates to a mass production system for synthesized carbon nanotubes using a vapor synthesis method, and a mass production method thereof using the same.
  • the carbon nanotubes are composed of graphite sheets wound in a cylindrical shape, and can be classified into single-wall carbon nanotubes, double-wall carbon nanotubes, and multi-wall carbon nanotubes according to the number of graphite sheets.
  • Carbon nanotubes are anticipated to be useful in a wide variety of applications, for example, electronic information industry, energy industry, high performance composite materials, ultra-fine nano components, etc., in view of their light weight, excellent electrical and mechanical properties, chemical stability, and easy surface reaction. Accordingly, it is necessary to provide a method for synthesizing highly pure carbon nanotubes at low costs in mass production.
  • representative methods for synthesizing the carbon nanotubes include an arc-discharge method, a laser deposition method, a chemical vapor deposition method, and a vapor synthesis method.
  • an arc-discharge method or the laser deposition method since amorphous materials are generated along with the carbon nanotubes when synthesizing the carbon nanotubes, it is necessary to perform a thermal or chemical refinement process in order to obtain highly pure carbon nanotubes, and it is difficult to accomplish economical mass production.
  • the chemical vapor deposition method although it is possible to synthesize highly pure carbon nanotubes by aligning them on a substrate, it is also difficult to accomplish their mass production.
  • the vapor synthesis method has been spotlighted as a method for synthesizing the carbon nanotubes at low costs.
  • various vapor synthesis methods have been developed, there is a problem in that the carbon nanotubes synthesized by the conventional vapor synthesis methods comprises a high quantity of amorphous carbon particles, making it difficult to refine the carbon nanotubes.
  • the vapor synthesis methods are considered inappropriate for mass production of, especially, the single-wall or double-wall carbon nanotubes in terms of their significantly low yield, and high quantity of amorphous carbon particles contained in the synthesized carbon nanotubes.
  • the mass production system of the carbon nanotubes employing the vapor synthesis process is a batch type system in which the carbon nanotubes are synthesized by repeating a series of steps of inputting a metal catalyst into a reaction chamber, heating the reaction chamber for a predetermined period of time, and then cooling the reaction chamber for every batch.
  • a mass production system has problems in terms of high manufacturing costs and significantly low productivity due to repetition of the individual steps as described above for every batch, and of low uniformity of the carbon nanotubes due to difficulty of obtaining the same process conditions for every batch. Disclosure of Invention Technical Problem
  • Carbon nanotubes are anticipated to be useful in a wide variety of applications, for example, electronic information industry, energy industry, high performance composite materials, ultra-fine nano components, etc., in view of their light weight, excellent electrical and mechanical properties, chemical stability, and easy surface reaction. Accordingly, it is necessary to provide a method for synthesizing highly pure carbon nanotubes in a large quantity at low costs.
  • the present invention has been made to solve the above problems, and it is an object of the present invention to provide a mass production system and method for synthesizing carbon nanotubes via a vapor synthesis process in an open-type reaction chamber.
  • the present invention relates to a mass production system for synthesized carbon nanotubes, configured to completely open the reaction chamber to an outside while the carbon nanotubes are being synthesized in the reaction chamber, and to block introduction of external air into the reaction chamber via difference in gravities of gases, and a mass production method thereof.
  • the carbon nanotubes having various properties can be synthesized in a large amount by controlling conveying speed of catalyst, reaction temperature, particle size of metal catalyst, injection amount of carbon source gas, and injection amount of hydrogen.
  • a mass production system for synthesized carbon nanotubes comprising: a reaction chamber having at least one opening opened to external air, and at least one different-specific gravity gas occupying region filled with a different specific gravity gas having a different specific gravity from that of the external air to block the external air from being introduced into the reaction chamber through the opening; a carbon nanotube synthesizing unit positioned in the different- specific gravity gas occupying region to synthesize the carbon nanotubes by the medium of a catalyst introduced thereto through the opening; a conveying unit to convey the catalyst to the carbon nanotube synthesizing unit through the opening; and gas supply unit to supply the different specific gravity gas and a carbon source gas used for synthesizing the carbon nanotubes to the different-specific gravity gas occupying region and the carbon nanotube synthesizing unit, respectively.
  • the opening comprises an inlet through which the catalyst is introduced into the reaction chamber, and an outlet through which the carbon nanotubes synthesized by the carbon nanotube synthesizing unit are discharged to an outside of the reaction chamber, and the conveying unit conveys the catalyst and/or the carbon nanotubes via the opening, the different-specific gravity gas occupying region, the carbon nanotube synthesizing unit, and the outlet.
  • the carbon nanotube synthesizing unit comprises a reaction region defined in the reaction chamber so as to be blocked from the external air by the different specific gravity gas filled in the different-specific gravity gas occupying region; a carbon source gas injector to inject the carbon source gas supplied from the gas supply unit to the reaction region such that the catalyst conveyed to the reaction region by the conveying unit reacts with the carbon source gas to synthesize the carbon nanotubes; and a heating member to heat the reaction region.
  • the reaction region of the carbon nanotube synthesizing unit is defined at a lower portion of at least one region in the different-specific gravity gas occupying region filled with a different specific gravity gas having a lower specific gravity than the carbon source gas, and the carbon nanotube synthesizing unit further comprises a carbon source gas restriction part opened at an upper portion to block the carbon source gas injected to the reaction region from escaping from the reaction region.
  • the different-specific gravity gas occupying region comprises a first different-specific gravity gas occupying region filled with a different specific gravity gas having a lower specific gravity than the carbon source gas; and a second different- specific gravity gas occupying region filled with a different specific gravity gas having a higher specific gravity than that of the carbon source gas, the first different-specific gravity gas occupying region, the reaction region, and the second different-specific gravity gas occupying region being sequentially defined in a gravity direction within the reaction chamber.
  • the different specific gravity gas comprises at least one of a gas having a lower specific gravity than that of the external air, and a gas having a higher specific gravity than that of the external air in order to block the external air from being introduced into the reaction chamber through the opening depending on a location of the opening on the reaction chamber.
  • the system further comprises a heating member to heat at least one region inside the reaction chamber to reduce the catalyst introduced into the reaction chamber through the opening, and at least one of the different specific gravity gases occupying the different-specific gravity gas occupying regions is hydrogen gas.
  • the carbon source gas injector comprises a plurality of nozzles dispersedly arranged corresponding to a dimension of the reaction region to uniformly inject the carbon source gas into the reaction region.
  • the reaction chamber has at least one discharge pipe formed therein to discharge hydrogen gas to the outside of the reaction chamber in order to accomplish an equilibrium state between pressure of the hydrogen gas occupying the different-specific gravity gas occupying region and pressure of the external air.
  • the mass production system further comprises a cooling unit to cool one region of the reaction chamber near the outlet such that the carbon nanotubes are cooled by the cooling unit.
  • a mass production method of synthesized carbon nanotubes comprising the steps of: supplying a catalyst into a reaction chamber having at least one opening opened to external air, through which the catalyst is supplied to the reaction chamber, and at least one different- specific gravity gas occupying region filled with a different specific gravity gas having a different specific gas from that of the external air to block the external air from being introduced into the reaction chamber through the opening; supplying a carbon source gas to the reaction chamber to allow the carbon source gas to react with the catalyst in the reaction region blocked from the external air by the different specific gas, thereby synthesizing the carbon nanotubes; and discharging the synthesized carbon nanotubes to an outside of the reaction chamber through the opening.
  • the method further comprises supplying hydrogen gas into the reaction chamber to allow the hydrogen gas to react with the catalyst, thereby reducing the catalyst.
  • the method further comprises discharging a portion of the hydrogen gas through a discharge pipe formed in the reaction chamber in order to accomplish an equilibrium state between pressure of the hydrogen gas occupying the different-specific gravity gas occupying region and pressure of the external air.
  • the present invention can be applied to the mass production system for synthesized carbon nanotubes using the vapor synthesis method.
  • the present invention can be applied to the mass production method of synthesized carbon nanotubes employing the mass production system for synthesized carbon nanotubes, which comprises an open-type reaction chamber.
  • Fig. 1 is a schematic cross-sectional view illustrating a mass production system for synthesized carbon nanotubes in accordance with a first embodiment of the present invention
  • Fig. 2 is a schematic cross-sectional view illustrating a mass production system for synthesized carbon nanotubes in accordance with a second embodiment of the present invention
  • Fig. 3 is a schematic cross-sectional view illustrating a mass production system for synthesized carbon nanotubes in accordance with a third embodiment of the present invention
  • Fig. 4 is a schematic cross-sectional view illustrating a mass production system for synthesized carbon nanotubes in accordance with a fourth embodiment of the present invention.
  • Fig. 1 is a schematic cross-sectional view illustrating a mass production system for synthesized carbon nanotubes in accordance with a first embodiment of the present invention.
  • the mass production system for synthesized carbon nanotubes according to the first embodiment comprises a reaction chamber 1 having a predetermined space defined therein.
  • the reaction chamber 1 has an inlet 2, and an outlet 3 formed at one side thereof. Both inlet 2 and outlet 3 of the reaction chamber have an open type structure which is opened to atmosphere.
  • the system further comprises a conveying unit 15 which conveys a bucket 10, that is, a catalyst containing member which contains a metal catalyst, from the inlet 2 to the outlet 3 via the interior of the reaction chamber 1.
  • the reaction chamber 1 has an upright structure.
  • the reaction chamber 1 comprises the inlet 2 opened downwardly at one side, a metal catalyst reduction unit 100 extending upwardly from the inlet 2 of the reaction chamber, a carbon nanotube synthesizing unit 200 connected with the metal catalyst reduction unit 100 and extending downwardly therefrom, a cooling unit 300 connected with the carbon nanotube synthesizing unit 200 at a lower portion of the reaction chamber 1, and the outlet 3 connected with the cooling unit 300 and opened upwardly.
  • the metal catalyst reduction unit 100, the carbon nanotube synthesizing unit 200 and/or the cooling unit 300 are connected with a gas supply unit 50, which supplies carbon source gas, hydrogen gas, argon gas (or other inert gas such as nitrogen gas) and the like into the reaction chamber.
  • the reaction chamber has the structure wherein the inlet 2, the metal catalyst reduction unit 100, the carbon nanotube synthesizing unit 200, the cooling unit 300, and the outlet 3 are sequentially connected with each other.
  • the metal catalyst reduction unit 100 serves to remove oxygen from a metal oxide catalyst introduced into the reaction chamber 1 by reducing the metal oxide catalyst.
  • the metal catalyst reduction unit 100 comprises an upper reaction chamber 110 having a space defined therein, and a first heating member 150 provided on the upper reaction chamber 110.
  • the metal catalyst reduction unit 100 is provided with a hydrogen gas discharge pipe 120 at one side above the inlet 2 of the reaction chamber such that the hydrogen gas discharge pipe 120 is exposed to external air.
  • the upper reaction chamber 110 is closed at an upper side to confine a gas rising within the reaction chamber.
  • the first heating member 150 is a heat generating mechanism to heat the interior of the reaction chamber, and is provided with a temperature sensor (not shown) to maintain the interior of the reaction chamber at a temperature of 600 ⁇ 1,200 °C.
  • the upper reaction chamber 110 of the metal catalyst reduction unit 100 is occupied with hydrogen gas supplied into the reaction chamber.
  • An occupation region of the upper reaction chamber 110 occupied with hydrogen gas having the lowest specific gravity among several gases in the reaction chamber will be referred to as a hydrogen gas occupation region.
  • the metal oxide catalyst is provided in the form of catalyst carrier which contains the metal oxide catalyst. [37]
  • the metal catalyst reacts with the carbon source gas, synthesizing the carbon nanotubes.
  • the carbon nanotube synthesizing unit 200 comprises a central reaction chamber 210 having an upright space to allow a gas having a lower specific gravity to rise therein, and a second heating member 250 installed to the central reaction chamber 210.
  • the central reaction chamber 210 Since the central reaction chamber 210 is provided with a reaction region where the metal catalyst reacts with the carbon source gas, thereby allowing synthesis of the carbon nanotubes, the central reaction chamber 210 has an enough length to allow the metal catalyst to pass therethrough for a sufficient period of time, and has an inner diameter greater than the upper reaction chamber 110 or a lower reaction chamber 310 described below in order to ensure that a sufficient amount of carbon source gas exists therein.
  • the second heating member 250 is also a heat generating mechanism to heat the interior of the reaction chamber, and is provided with another temperature sensor (not shown) to maintain the interior of the reaction chamber at a temperature of 600 ⁇ 1,200 °C.
  • the central reaction chamber 210 constituting the carbon nanotube synthesizing unit 200 is occupied with the carbon source gas, for example, ethylene gas, having a higher specific gravity than that of hydrogen gas.
  • An occupation region of the central reaction chamber 210 occupied with ethylene gas having the higher specific gravity than hydrogen gas among several gases in the reaction chamber will be referred to as an ethylene gas occupation region.
  • the central reaction chamber 210 has been described as an exemplary structure which allows the gases to ascend or descend according to difference in specific gravities thereof.
  • the central reaction chamber 210 is not limited to a slope shown in Fig. 1, and may comprise any structure which has a suitable slope formed therein as long as it enables the gases to ascend or descend according to difference in specific gravities thereof.
  • the cooling unit 300 serves to cool the synthesized carbon nanotubes.
  • the cooling unit 300 comprises a lower reaction chamber 310 connected with the carbon nanotube synthesizing unit 200 and having a closed bottom surface to allow a gas, for example, argon gas, heavier than the carbon source gas to remain thereon, and a cooling member 350 provided to the lower reaction chamber 310.
  • the lower reaction chamber 310 constituting the cooling unit 300 is filled with argon gas which is one of inert gases having heavier specific gravities than that of ethylene gas, and an occupation region of the lower reaction chamber 310 occupied with argon gas will be referred to as an argon gas occupation region.
  • the cooling member 350 is constituted by a water cooling jacket.
  • various cooling members 350 may be used as long as they can perform a cooling function.
  • the lower reaction chamber 310 is formed at an inside bottom with a U-shaped discharge pipe 20 which discharges byproducts including water. Since the U-shaped discharge pipe 20 has water pooling in a bent structure of the U shape, the gas cannot escape from the lower reaction chamber 310.
  • the cooling unit 300 decreases the temperature of argon gas so that the specific gravity of argon gas is prevented from being lowered due to thermal expansion.
  • the gas supply unit 50 comprises a carbon source gas tank, an argon gas or nitrogen gas tank, and a hydrogen gas tank, each of which is connected with the reaction chamber via a gas injection pipe having an opening/closing valve.
  • Each of the tanks comprises a purifier.
  • the purifiers purify a mixture of carbon gas and a mixture of hydrogen gas, and supply highly pure carbon source gas and hydrogen gas.
  • Examples of the carbon source gas include methane, ethane, ethylene, acetylene, propylene, butane, butylenes, butadiene, hexane, heptane, toluene, benzene, xylene, gasoline, propane, liquid propane gas (LPG), liquid natural gas (LNG), naphtha, carbon monoxide, and alcohol-based gas.
  • the inert gas is contained in the lower reaction chamber 310.
  • the present invention may use any one of the inert gases heavier than the carbon source gas without being limited to argon or nitrogen.
  • the carbon source gas moves upwards, and is positioned in the carbon nanotube synthesizing unit 200, while hydrogen gas moves upwards, passes the carbon nanotube synthesizing unit 200, and is then positioned in the metal catalyst reduction unit 100.
  • hydrogen gas collides with, and causes the carbon source gas filled in the carbon nanotube synthesizing unit 200 to move while rising and passing through the carbon nanotube synthesizing unit 200, the moving carbon source gas is actively brought into contact with the metal catalyst, thereby enabling more active synthesis of the carbon nanotubes.
  • the conveying unit 15 serves to convey the catalyst containing member from the inlet 2 to the outlet 3 of the reaction chamber, and is configured to circulate within the reaction chamber.
  • the conveying unit 15 can control a conveying speed of the catalyst containing member via motor control or the like so that a reduction time of the metal oxide catalyst and a synthesis time of the carbon nanotubes can be freely controlled.
  • the catalyst containing member according to the embodiment is a bucket to supply the metal catalyst required for synthesis of the carbon nanotubes via a vapor synthesizing method to the reaction chamber.
  • the bucket is hingably connected at an upper end with a conveyer system.
  • the bucket is maintained in an upright state at any locations by hinge coupling so that the metal catalyst contained in catalyst containing member is not poured out of the catalyst containing member.
  • the catalyst containing member is not limited to the bucket, and can be realized in various forms appropriate for conveying the metal catalyst.
  • the catalyst containing member may be made of various materials, such as metal, quartz, graphite, and the like.
  • the catalyst containing member may have an aperture formed at a bottom surface thereof to enable active reaction of the metal catalyst with the carbon source gas.
  • the mass production system of this embodiment has been described as employing the bucket as for the catalyst containing member which contains the metal catalyst, the present invention is not limited to this structure.
  • the mass production system of the invention may employ various members, such as a boat or a tray, which can contain the metal catalyst.
  • Step 1 200 of the reaction chamber 1 are heated to a desired temperature, for example, to a temperature of 600 ⁇ 1,200 °C by the first heating member 110 and the second heating member 210 (Step 1).
  • an inert gas for example, argon gas or nitrogen gas
  • an inert gas injection pipe connected with the upper reaction chamber 110 argon gas having a higher specific gravity than external air causes air existing in the interior of the reaction chamber to be discharged to the outside of the reaction chamber via the inlet 2 and the outlet 3 while moving to a left or right side of the upper reaction chamber 110. In this manner, air or oxygen is completely discharged from the reaction chamber 1, so that an inert gas atmosphere is formed in the reaction chamber 1.
  • a metal oxide catalyst, or the bucket 10 receiving a catalyst bearing material which comprises the metal oxide catalyst is supplied from the outside into the reaction chamber through the inlet 2 (Step 4).
  • the bucket 10 is conveyed by the conveying unit 15.
  • the catalyst bearing material may have a powder shape, and comprise magnesium oxide (MgO), alumina (Al O ), zeolite, silica or the like.
  • a sol-gel method, a precipitation method or an impregnation method may be used as a sol-gel method.
  • the metal oxide catalyst of the bucket 10 conveyed into the reaction chamber is reduced to a metal catalyst by the metal catalyst reduction unit 100 (Step 5).
  • the metal oxide catalyst is an iron oxide
  • the iron oxide reacts with hydrogen gas, and is converted into pure iron and water.
  • a metal oxide catalyst includes Co, Ni, Mo or alloys thereof as well as iron.
  • the metal catalyst of the bucket 10 After passing through the metal catalyst reduction unit 100, the metal catalyst of the bucket 10 is conveyed to the carbon nanotube synthesizing unit 200.
  • the metal catalyst reacts with a carbon source gas in the carbon nanotube synthesizing unit 200, synthesizing carbon nanotubes (Step 6).
  • the metal catalyst particles are born and secured to the nano-sized pores of the powdery catalyst bearing material so that the metal catalyst particles are suppressed from moving even at high temperatures required for synthesizing the carbon nanotubes, thereby enabling synthesis of carbon nanotubes having a uniform diameter.
  • the carbon nanotubes are synthesized with the metal catalyst particles, having a size of several nano meters, born and secured to the nano- sized pores of the powdery matrix, the synthesized carbon nanotubes are highly pure without amorphous carbon clusters formed therein.
  • the bucket 10 carrying the synthesized carbon nanotubes is conveyed to the cooling unit 300, and is forcibly cooled to room temperature by the cooling member 350 (Step 7).
  • the carbon nanotubes may be discharged to the outside of the reaction chamber, and then cooled at the outside without performing such a cooling process.
  • the synthesized carbon nanotubes are discharged to the outside of the reaction chamber through the outlet 3 (Step 8).
  • the bucket 10 with a new metal catalyst received therein is conveyed into the reaction chamber via the inlet 2.
  • Operation to withdraw the synthesized carbon nanotubes from the bucket, and then input a new metal catalyst thereto can be performed by typical automation equipment known in the art.
  • the mass production system for synthesized carbon nanotubes comprises the metal catalyst reduction unit 100, the carbon nanotube synthesizing unit 200 and the cooling unit 300 successively arranged, and has the open structure opened to the external air, it is possible to synthesize the carbon nanotubes continuously.
  • the present invention accomplishes synthesis of the carbon nanotubes via a continuous process which enables continuous input of the metal catalyst into the reaction chamber and continuous discharge of the synthesized carbon nanotubes from the reaction chamber to the outside.
  • Hydrogen gas having a high temperature is collected in the metal catalyst reduction unit 100 above the inlet 2. Since the high temperature hydrogen gas has a lower specific gravity than that of the external air, the air is always located under hydrogen gas, which prevents the external air from permeating into the reaction chamber 1. Specifically, assuming that the interior of the reaction chamber 1 remains at a temperature of about 900 °C, and the exterior of the reaction chamber 1 has a temperature of about 20 °C.
  • a predetermined amount of hydrogen gas introduced into the reaction chamber is discharged to the outside of the reaction chamber through the hydrogen gas discharge pipe 120 of the upper reaction chamber 110. This is for the purpose of securely preventing the external air from permeating into the reaction chamber by providing an equilibrium state between pressures of hydrogen gas and the external air at a region where hydrogen gas in the inlet 2 of the reaction chamber is brought into contact with the external air.
  • this structure is configured to obtain equilibrium between hydrogen gas and the external air at the inlet of the reaction chamber by allowing the predetermined amount of hydrogen gas to be discharged through the separate the hydrogen gas discharge pipe 120 in order to allow an increase in pressure of hydrogen gas by an excessive amount of hydrogen gas injected into the reaction chamber through the gas injection pipe while preventing hydrogen gas from being discharged to the outside through the inlet 2 due to the increase in pressure of hydrogen gas. That is, although the predetermined amount of hydrogen gas reacts with the metal oxide catalyst upon reduction of the metal oxide catalyst, the pressure of hydrogen gas remains at a predetermined value or more within the reaction chamber by injecting hydrogen gas more than a reacted amount of hydrogen gas into the reaction chamber.
  • the mass production system of the synthesized carbon nanotubes allows various gases having different specific gravities to occupy specified regions of the reaction chamber so that external air cannot infiltrated into the reaction chamber even with the open structure of the system in which the reaction chamber is completely open.
  • the carbon nanotubes are synthesized after filling the reaction chamber with an inert gas to discharge oxygen and the air to the outside from the reaction chamber with the interior thereof completely blocked from the outside in order to form an oxygen-free interior of the reaction chamber.
  • reaction atmosphere required for synthesis of the carbon nanotubes is achieved and maintained only with preparation for synthesis of the carbon nanotubes at an initial stage. Accordingly, with the mass production system for synthesized carbon nanotubes according to the invention, the carbon nanotubes can be continuously synthesized without being stopped even for an instant once the system is operated.
  • Such continuous synthesis of the carbon nanotubes can be achieved by the system of the present invention since the metal catalyst is continuously fed into the reaction chamber which is completely opened. That is, even at a moment when the metal catalyst is fed from the exterior into the reaction chamber, the carbon nanotubes are synthesized continuously in the carbon nanotube synthesizing unit 200.
  • a specified gas of a predetermined region in the reaction chamber serves to completely block introduction of the external air into the reaction chamber. That is, gases having different specific gravities occupy specified regions within the reaction chamber, respectively, so that each gas blocks other gases from permeating into its specified region inside the reaction chamber, thereby preventing the external air from permeating into the reaction chamber. Since the gas occupying the specified region of the reaction chamber is in an equilibrium state in pressure with the external air, the external air is prevented from permeating into the reaction chamber.
  • Fig. 2 is a schematic cross-sectional view illustrating a mass production system for synthesized carbon nanotubes according to a second embodiment of the present invention.
  • the mass production system of the second embodiment comprises a reaction chamber 1 having a heating member and a passage 4 with an inner space defined therein to communicate with an outside of the reaction chamber, and a conveying unit 15 to convey a metal catalyst into the reaction chamber 1 through the passage 4.
  • the reaction chamber 1 of the mass production system according to this embodiment has the passage 4 open downwardly, and a carbon nanotube synthesizing unit 200 formed above the passage 4 inside the reaction chamber.
  • the reaction chamber is provided with a gas supply unit 50, which comprises gas tanks and gas injection pipes, each connecting an associated gas tank with the reaction chamber and having an opening/closing valve, to supply carbon source gas, hydrogen gas, and an inert gas into the reaction chamber, respectively.
  • a gas supply unit 50 which comprises gas tanks and gas injection pipes, each connecting an associated gas tank with the reaction chamber and having an opening/closing valve, to supply carbon source gas, hydrogen gas, and an inert gas into the reaction chamber, respectively.
  • the carbon nanotube synthesizing unit 200 comprises a shower head 230 connected with a carbon source gas tank at an upper portion of the reaction chamber 1 and having plural injection nozzles arranged to allow uniform injection of a carbon source gas, a carbon source gas restriction part 280 positioned below the shower head 230 and opened at an upper portion, such as a box without an upper surface, to collect the carbon source gas, and a heating member 250 installed to the reaction chamber.
  • the carbon source gas restriction part 280 has a box structure which is surrounded by a wall having a predetermined height, and opened only at an upper portion thereof.
  • the shower head 230 is positioned deeper from an upper end of the wall of the carbon source gas restriction part 280. With this structure, after being injected from the shower head 230, the carbon source gas remains inside the carbon source gas restriction part 280. A portion of the carbon source gas overflowing from the carbon source gas restriction part 280 exists mainly at a lower space within the reaction chamber.
  • the shower head has an enough area to cover most area of the opened upper portion of the carbon source gas restriction part.
  • the carbon nanotube synthesizing unit has a space for allowing entrance of a catalyst containing member into the carbon source gas restriction part, and a space for allowing exit of the catalyst containing member from the carbon source gas restriction part between the shower head and the carbon source gas restriction part. Accordingly, the shower head very efficiently prevents hydrogen having a lighter weight than the carbon source gas from entering the carbon source gas restriction part while allowing entrance and exit of the catalyst containing member into and from the carbon source gas restriction part, thereby maintaining high synthesizing yield of the carbon nanotubes.
  • the carbon source gas restriction part 280 has a leeway space defined at an upper portion to allow a bucket, that is, the catalyst containing member, to enter through the upper portion at one side and to leave through the upper portion at the other side.
  • a bucket that is, the catalyst containing member
  • the carbon source gas positioned in the carbon source gas restriction part reacts with the metal catalyst in a reaction region formed below hydrogen gas occupying the leeway space above the carbon source gas restriction part.
  • the carbon source gas restriction part 280 is formed with a discharge pipe 285 through which water, a residual carbon source gas, and other by-products can be discharged. If the carbon source gas is excessively supplied into the reaction chamber, a portion of the carbon source gas is discharged to the outside through the discharge pipe 285.
  • the carbon source gas restriction part 280 serves to collect the carbon source gas heavier than hydrogen gas, and is not limited to the box structure. Alternatively, the carbon source gas restriction part 280 has various structures, which have an opened upper portion, a closed periphery, and the bottom surface.
  • the heating member attached to the reaction chamber heats the whole interior of the reaction chamber.
  • a metal oxide catalyst in the bucket 10 is reduced via reaction with hydrogen gas injected through the gas injection pipe and filled in the reaction chamber before the bucket 10 reaches the carbon source gas restriction part 280, so that oxygen is removed from the reaction chamber.
  • the reaction chamber itself filled with hydrogen gas serves as the metal catalyst reduction unit which reduces the metal catalyst.
  • the reaction chamber is formed with a separate reduction inducing guide surface contacting one side of the carbon source gas restriction part in order to ensure reduction of the metal catalyst.
  • the reduction inducing guide surface has a sufficient length in a lateral direction, and enables the metal oxide catalyst of the catalyst containing member to be reduced while moving for a sufficient time along an upper space of the reaction chamber.
  • the conveying unit is disposed to have a suitable conveyance path such that the catalyst containing member moves a sufficiently long distance along the upper portion of the reaction chamber before reaching the carbon source gas restriction part, allowing the metal oxide catalyst to be reduced for a sufficient time.
  • the passage 4 extends a predetermined distance downwardly from the reaction chamber.
  • the reaction chamber further comprises a cooling unit 300 which is formed around the passage 4, and comprises a cooling member 250 to cool the carbon nanotubes when the carbon nanotubes are discharge from the reaction chamber to the outside after being synthesized therein.
  • a hydrogen gas discharge pipe 120 is formed at one side of the passage 4. If hydrogen gas is excessively supplied from the gas supply unit 50, the pressure of hydrogen gas continues to increase. Thus, it is necessary to discharge a predetermined amount of hydrogen gas to the outside of the reaction chamber in order to maintain equilibrium between the pressures of hydrogen gas and external air at a region where hydrogen gas of the passage 4 contacts the external air. To this end, hydrogen gas is discharged through the hydrogen gas discharge pipe 120 instead of the passage 4.
  • the reason that the hydrogen gas discharge pipe 120 is formed at a lower portion of the reaction chamber is that, when hydrogen gas rises to an upper portion of the reaction chamber at a high temperature condition in the reaction chamber, hydrogen gas is prevented from being immediately discharged to the outside, but is sufficiently filled in the reaction chamber, thereby sufficiently increasing the pressure of hydrogen gas within the reaction chamber.
  • an argon gas injection pipe is connected with the shower head of the reaction chamber.
  • Fig. 3 is a schematic cross-sectional view illustrating a mass production system for synthesized carbon nanotubes according to a third embodiment of the invention.
  • the mass production system of the third embodiment is the same as that of the second embodiment in that it enables entrance and exit of a bucket 10, that is, the catalyst containing member, through a passage 4.
  • the third embodiment is different from the second embodiment, particularly, in that the passage 4 is open upwardly, and is connected with a U-shaped part 300.
  • the mass production system of the third embodiment further comprises a conveying unit 15 which conveys the bucket 10 containing a metal oxide catalyst into a reaction chamber to synthesize carbon nanotubes, and then conveys the bucket to the outside of the reaction chamber.
  • the U-shaped part 400 is formed downwardly from the passage 4, bent and horizontally extends a predetermined length, and is then connected at an extended end with a carbon nanotube synthesizing unit 200 serving to synthesize the carbon nanotubes.
  • the U-shaped part 400 constitutes a cooling unit 300 which comprises a cooling member 350 disposed around the U-shaped part 400.
  • a metal catalyst reduction unit 100, and the carbon nanotube synthesizing unit 200 are formed within the reaction chamber.
  • the U-shaped part 400 is filled with argon gas injected through an argon gas injection pipe of a gas supply unit 50 up to a predetermined height, while being cooled by the cooling member 350.
  • the cooled argon gas is considerably increased in specific gravity greater than air outside the reaction chamber.
  • the external air is always located above argon gas having the higher specific gravity at the passage 4 of the reaction chamber, thereby blocking the external air from permeating into the reaction chamber 1.
  • the gas occupying the U-shaped part 400 may be any of inert gases having a higher specific gravity than that of the external air as well as argon gas.
  • the reaction chamber has a horizontal extension part 105, which is bent from the
  • the horizontal extension part 105 hydrogen gas injected into the reaction chamber through hydrogen gas injection pipe reacts with a metal oxide catalyst introduced into the horizontal extension part 105 of the reaction chamber by the conveying unit 15 so that oxygen is removed from the metal oxide catalyst.
  • the catalyst containing member After passing through the horizontal extension part 105, the catalyst containing member is conveyed adjacent to a ceiling surface of a rear reaction chamber 105.
  • the horizontal extension part 105 is not limited to the length shown in Fig. 3, and has enough length to allow the metal oxide catalyst to be reduced for a sufficient time.
  • the rear reaction chamber 205 connected with the horizontal extension part 105 has a space of a predetermined size defined therein, and a shower head 230 installed at an upper portion to uniformly inject a carbon source gas thereto.
  • the rear reaction chamber 205 is provided at the upper portion with a hydrogen gas discharge pipe 207 through which hydrogen, being lighter than the carbon source gas, is discharged to the outside, and at a lower portion with a heating member 250.
  • the metal oxide catalyst in the catalyst containing member conveyed into the rear reaction chamber 150 by the conveying unit 15 reacts with the carbon source gas while passing below the shower head 230, and synthesizes carbon nanotubes. With the synthesized carbon nanotubes contained therein, the catalyst containing member is discharged to the outside of the reaction chamber along the same path by the conveying unit 15.
  • the rear reaction chamber 205 has a bottom surface deeper than the horizontal extension part 105, and the shower head 230 is set adjacent to the bottom surface of the rear reaction chamber 205.
  • the rear reaction chamber 205 allows the carbon source gas to accumulate in a predetermined space on the bottom, which constitutes a reaction region where the metal catalyst reacts with the carbon source gas. Since the metal catalyst passes directly above the bottom of the rear reaction chamber 205, it reacts with the carbon source gas densely accumulated thereon, thereby actively synthesizing the carbon nanotubes.
  • the bottom of the rear reaction chamber 205 is formed deeper than the horizontal extension part 205 for the purpose of enhancing reaction efficiency by forcing the carbon source gas heavier than hydrogen gas to be accumulated in the lower space of the rear reaction chamber 205 via gravity.
  • Fig. 4 is a schematic cross-sectional view illustrating a mass production system for synthesized carbon nanotubes in accordance with a fourth embodiment of the invention.
  • the mass production system according to the fourth embodiment is the same as that of the third embodiment except that the mass production system of the fourth embodiment does not comprise the U-shaped part, and has a downwardly open passage.
  • the mass production system of the fourth embodiment is different from the third embodiment in that a hydrogen gas discharge pipe 207 is formed upper portion of the passage. With the hydrogen gas discharge pipe 207 formed near the passage, hydrogen gas is prevented from being discharged through the passage.
  • heating member and the cooling member 250 are described as being installed at the outside of the reaction chamber, the present invention is not limited to this structure. Instead, these components can be installed at any suitable locations for heating and cooling.
  • the mass production system may comprise one or more different-specific gravity gas occupying parts according to the shape of the reaction chamber.
  • the different-specific gravity gas occupying parts separated from each other may be occupied with the same gas or different gases.
  • a mechanism for conveying the catalyst containing member may be not only a conveyor, but also any of various well-known conveying members.
  • the carbon source gas restriction part 280 in the reaction chamber is provided for the purpose of enhancing efficiency of synthesizing the carbon nanotubes, and serves to accumulate the carbon source gas on a specific location.
  • the embodiment of the invention comprises a separate cooling member to cool the synthesized carbon nanotubes to room temperature
  • the invention is not limited to this structure, and thus the carbon nanotubes may be cooled at the outside after being discharged from the reaction chamber instead of using the cooling member.
  • the present invention can be used for the mass production system of carbon nanotubes using a vapor synthesis process.
  • the present invention can be used for the method of synthesizing the carbon nanotubes in a great quantity using the mass production system comprising an open type reaction chamber.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention concerne un système et un procédé de production industrielle de nanotubes de carbone synthétisés. Ce système est agencé de façon à ouvrir complètement la chambre de réaction sur l'extérieur pendant la synthèse de nanotubes de carbone effectuée dans cette chambre tout en permettant à un gaz spécifique d'occuper une région prédéterminée à l'intérieur de cette chambre de réaction, bloquant ainsi l'introduction d'air extérieur dans la chambre de réaction qui est néanmoins ouverte sur l'air extérieur. Ce système comprend une chambre de réaction possédant au moins une ouverture ouverte sur l'air extérieur et au moins une région occupée par un gaz de gravité spécifique différente remplie avec un gaz de gravité spécifique différente possédant une gravité spécifique différente de celle de l'air extérieur afin d'empêcher cet air extérieur d'entrer dans la chambre de réaction par l'ouverture, une unité de synthèse de nanotubes de carbone placée dans la région occupée par le gaz de gravité spécifique différente permet de synthétiser des nanotubes de carbone via un catalyseur introduit dans cette région à travers l'ouverture, une unité transporteur permet de transporter le catalyseur dans l'unité de synthèse de nanotubes de carbone par l'ouverture et, une unité d'alimentation de gaz permet d'alimenter le gaz de gravité spécifique différente et un gaz de source carbone utilisé pour synthétiser les nanotubes de carbone vers la région occupée par le gaz de gravité spécifique différente et une unité de synthèse de nanotubes de carbone, respectivement.
PCT/KR2006/000541 2005-02-17 2006-02-17 Systeme de fabrication industrielle de nanotubes de carbone et procede de fabrication industrielle Ceased WO2006088322A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2005-0013266 2005-02-17
KR1020050013266A KR100649744B1 (ko) 2005-02-17 2005-02-17 탄소나노튜브 대량합성장치 및 대량합성방법

Publications (1)

Publication Number Publication Date
WO2006088322A1 true WO2006088322A1 (fr) 2006-08-24

Family

ID=36916691

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2006/000541 Ceased WO2006088322A1 (fr) 2005-02-17 2006-02-17 Systeme de fabrication industrielle de nanotubes de carbone et procede de fabrication industrielle

Country Status (2)

Country Link
KR (1) KR100649744B1 (fr)
WO (1) WO2006088322A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2352523C1 (ru) * 2007-06-26 2009-04-20 Андрей Алексеевич Александров Устройство для получения углеродных нанотрубок
US7744793B2 (en) 2005-09-06 2010-06-29 Lemaire Alexander B Apparatus and method for growing fullerene nanotube forests, and forming nanotube films, threads and composite structures therefrom
US7850778B2 (en) 2005-09-06 2010-12-14 Lemaire Charles A Apparatus and method for growing fullerene nanotube forests, and forming nanotube films, threads and composite structures therefrom
US10961618B2 (en) 2014-07-16 2021-03-30 Imperial College Innovations Limited Process for producing carbon-nanotube grafted substrate
RU2805570C1 (ru) * 2022-05-19 2023-10-19 ЮГ Инвестмент Лтд. Способ получения водорода без образования углекислого газа, устройство для его реализации и катализатор

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100860013B1 (ko) 2007-06-01 2008-09-25 주식회사 제이오 탄소나노튜브의 대량합성을 위한 회전 다단식 원통형 반응기
KR100956352B1 (ko) * 2007-09-06 2010-05-07 세메스 주식회사 탄소나노튜브 제조장치 및 그 방법
KR100980654B1 (ko) * 2008-09-08 2010-09-08 (주) 나노허브 탄소나노튜브 제조용 촉매의 제조방법

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6413487B1 (en) * 2000-06-02 2002-07-02 The Board Of Regents Of The University Of Oklahoma Method and apparatus for producing carbon nanotubes
US6759025B2 (en) * 2000-09-22 2004-07-06 Iljin Nanotech Co., Ltd. Method of synthesizing carbon nanotubes and apparatus used for the same
US6855301B1 (en) * 2000-10-20 2005-02-15 The Ohio State University Synthesis method for producing carbon clusters and structured carbon clusters produced thereby

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6413487B1 (en) * 2000-06-02 2002-07-02 The Board Of Regents Of The University Of Oklahoma Method and apparatus for producing carbon nanotubes
US6759025B2 (en) * 2000-09-22 2004-07-06 Iljin Nanotech Co., Ltd. Method of synthesizing carbon nanotubes and apparatus used for the same
US6855301B1 (en) * 2000-10-20 2005-02-15 The Ohio State University Synthesis method for producing carbon clusters and structured carbon clusters produced thereby

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7744793B2 (en) 2005-09-06 2010-06-29 Lemaire Alexander B Apparatus and method for growing fullerene nanotube forests, and forming nanotube films, threads and composite structures therefrom
US7850778B2 (en) 2005-09-06 2010-12-14 Lemaire Charles A Apparatus and method for growing fullerene nanotube forests, and forming nanotube films, threads and composite structures therefrom
US8162643B2 (en) 2005-09-06 2012-04-24 Lemaire Alexander B Method and apparatus for growing nanotube forests, and generating nanotube structures therefrom
US8551376B2 (en) 2005-09-06 2013-10-08 Grandnano, Llc Method for growing carbon nanotube forests, and generating nanotube structures therefrom, and apparatus
US8845941B2 (en) 2005-09-06 2014-09-30 Grandnano, Llc Apparatus for growing carbon nanotube forests, and generating nanotube structures therefrom, and method
US9815697B2 (en) 2005-09-06 2017-11-14 Grandnano, Llc Apparatus for growing carbon nanotube forests, and generating nanotube structures therefrom, and method
RU2352523C1 (ru) * 2007-06-26 2009-04-20 Андрей Алексеевич Александров Устройство для получения углеродных нанотрубок
US10961618B2 (en) 2014-07-16 2021-03-30 Imperial College Innovations Limited Process for producing carbon-nanotube grafted substrate
RU2805570C1 (ru) * 2022-05-19 2023-10-19 ЮГ Инвестмент Лтд. Способ получения водорода без образования углекислого газа, устройство для его реализации и катализатор

Also Published As

Publication number Publication date
KR100649744B1 (ko) 2006-11-27
KR20060091993A (ko) 2006-08-22

Similar Documents

Publication Publication Date Title
US8092754B2 (en) Carbon nanotubes mass fabrication system and mass fabrication method
US8597587B2 (en) Method and installation for the manufacture of carbon nanotubes
JP5081453B2 (ja) 方法
US7597869B2 (en) Method for producing carbon nanotubes
US20120251433A1 (en) Process for fabricating carbon nanotubes and apparatus for implementing the process
MX2014012551A (es) Metodos para utilizar catalizadores de metal en convertidores catalíticos de óxido de carbono.
JP2012519773A (ja) 圧気輸送の間の粒子への原子又は分子層堆積のための装置及び方法
KR100376202B1 (ko) 탄소나노튜브 또는 탄소나노섬유 합성용 기상합성 장치 및이를 사용한 합성방법
WO2006033367A1 (fr) Procédé et appareil de fabrication de nanostructure de carbone
WO2006088322A1 (fr) Systeme de fabrication industrielle de nanotubes de carbone et procede de fabrication industrielle
KR100732623B1 (ko) 탄소나노튜브 대량합성장치
KR102166813B1 (ko) 열교환식 반응관
KR100664546B1 (ko) 탄소나노튜브 대량합성장치
US7572413B2 (en) Apparatus for manufacturing carbon nanotubes
KR101082833B1 (ko) 탄소나노튜브 합성 장치
JPH0978360A (ja) 気相成長炭素繊維の製造方法
KR101016031B1 (ko) 탄소나노튜브 합성 장치
KR20090013310A (ko) 탄소나노튜브 합성 방법 및 장치
JP4782504B2 (ja) 微細炭素繊維の製造装置及びその製造方法
JP4736721B2 (ja) カーボンナノチューブの製造方法
US20250171866A1 (en) Molten Metal Reactors and Processes
TW200811032A (en) Carbon nanotubes mass fabrication system and mass fabrication method
WO1999043877A1 (fr) Procede et dispositif pour la fabrication de bobines en fibre de carbone
CN108778493A (zh) 粒子处理装置以及催化剂担载体和/或纤维状碳纳米结构体的制造方法
Raji et al. A computational model for predicting the mass transport in a CVD reactor for carbon nanotube synthesis

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06715992

Country of ref document: EP

Kind code of ref document: A1