WO2017057751A1 - カーボンナノチューブの製造装置および製造方法 - Google Patents
カーボンナノチューブの製造装置および製造方法 Download PDFInfo
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- WO2017057751A1 WO2017057751A1 PCT/JP2016/079159 JP2016079159W WO2017057751A1 WO 2017057751 A1 WO2017057751 A1 WO 2017057751A1 JP 2016079159 W JP2016079159 W JP 2016079159W WO 2017057751 A1 WO2017057751 A1 WO 2017057751A1
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Definitions
- the present invention relates to a technique for producing carbon nanotubes by a so-called chemical vapor deposition method (CVD method).
- CVD method chemical vapor deposition method
- Carbon nanotubes are new materials that are attracting attention from many fields because they have excellent properties such as conductivity, thermal conductivity, and mechanical strength. is there.
- CNTs are synthesized by placing carbon or a raw material containing carbon under high temperature conditions in the presence of a catalyst as necessary.
- a laser evaporation method, an arc discharge method and a chemical vapor deposition method are known.
- the chemical vapor deposition method that is, the CVD method
- Patent document 1 is mentioned as a prior art document regarding manufacture of CNT by CVD method.
- Patent Document 1 relates to a technique of a fluidized gas phase CVD method for producing CNTs in a flowing gas phase.
- An object of this invention is to provide the CNT manufacturing apparatus which can solve this subject.
- Another object of the present invention is to provide a CNT manufacturing method that can solve the above-mentioned problems.
- a carbon nanotube production apparatus for producing carbon nanotubes.
- the apparatus includes a cylindrical chamber, a carbon source supply unit that supplies a carbon source to the chamber from a carbon source supply port that opens to the chamber, and a non-oxidizing gas that flows from the gas supply port that opens to the chamber to the chamber.
- a gas supply unit for supplying gas an exhaust pipe configured to be able to discharge gas in the chamber from a gas vent, and a control valve provided in the exhaust pipe.
- the chamber is provided in a partial range in the cylinder axis direction of the chamber, is heated to a temperature at which carbon nanotubes are generated, and is downstream of the reaction zone and upstream of the gas vent.
- the apparatus closes the control valve and deposits the carbon nanotubes in the deposition zone when the physical property value indicating the deposition state of the carbon nanotubes detected by the deposition state detection unit is equal to or less than a predetermined threshold value.
- the control valve is opened to collect the carbon nanotubes deposited in the deposition zone.
- the “carbon nanotube (CNT)” refers to a tubular carbon allotrope (typically a cylindrical structure having a graphite structure), and is not limited to a special form (length or diameter). So-called single-walled CNTs, multi-walled CNTs, or carbon nanohorns having a square tube tip are typical examples included in the concept of CNT here. The technique disclosed here is particularly suitably used for the production of single-walled CNTs.
- upstream in the CNT manufacturing apparatus means upstream of the gas flow from the gas supply port to the gas vent
- downstream means the gas flow from the gas supply to the gas vent. Means downstream.
- the control valve is closed to deposit CNT in the deposition zone (typically, adhering to the inner wall of the chamber), so that the carbon source is better retained in the reaction zone upstream of the deposition zone. (In other words, diffusion to the downstream side of the reaction zone can be suppressed), and high-quality CNTs can be efficiently generated (for example, in high yield) from the carbon source.
- the CNT deposition proceeds to some extent in the deposition zone, the CNTs can be continuously manufactured by opening the control valve and collecting the CNT deposited in the deposition zone. That is, the apparatus having the above configuration is suitable for continuous production of CNTs.
- the apparatus further includes a collection unit for collecting the carbon nanotubes.
- the recovery unit is disposed downstream of the deposition zone and upstream of the gas vent. According to such a configuration, while the exhaust gas moves from the deposition zone to the gas vent, CNT that similarly moves from the deposition zone to the gas vent is collected by the collection unit. Therefore, CNT can be efficiently recovered.
- the recovery unit is disposed below the chamber. And it is comprised so that the carbon nanotube deposited in the said deposition zone may fall to the said collection
- CNT can be collected more efficiently by dropping the CNT with its own weight together with the flow of the exhaust gas.
- the physical property value indicating the deposition state of the carbon nanotube is the pressure in the chamber. In this way, it is possible to easily grasp the CNT deposition state in the deposition zone.
- the carbon source supply port is heated in the reaction zone (at the time of producing CNT, that is, a temperature at which CNT is generated when a carbon source is supplied from the supply port. ) Or in the vicinity thereof.
- CNT can be more efficiently produced
- the above configuration is advantageous in the case where a liquid material at normal temperature is used as the carbon source, and the liquid of the carbon source supplied from the carbon source supply port is gasified (vaporized) in a short time. Therefore, it can be preferably used for the production of CNTs using such a material as a carbon source.
- it is useful as an apparatus for producing CNTs using a liquid material (for example, toluene) at room temperature as the carbon source.
- the carbon source supply section extends in the reaction zone and is connected to the carbon source supply port (preferably disposed at or near the reaction zone).
- a source introduction tube is provided.
- the heat of the reaction zone is transmitted from the carbon source supply port through the wall surface of the carbon source introduction tube to the carbon source in the introduction tube, thereby shortening the carbon source (liquid) supplied from the carbon source supply port. It can be gasified in time.
- This is advantageous for continuous operation of the apparatus (that is, continuous production of CNT).
- CNT can be appropriately manufactured over a longer period of time.
- the gas supply unit includes a gas supply pipe extending in the reaction zone and connected to the gas supply port.
- the gas supply pipe and the carbon source introduction pipe have a double pipe structure in which the gas supply pipe is an outer pipe and the carbon source introduction pipe is an inner pipe.
- the non-oxidizing gas supplied from the gas supply port comes into contact with the carbon source (liquid) supplied from the carbon source supply port, and gasification and diffusion of the carbon source are promoted.
- the gas supply unit is configured to supply a carbon source gas together with a non-oxidizing gas from the gas supply port to the chamber. According to such a configuration, it is possible to efficiently generate CNTs whose diameter (for example, 2 nm or less, typically about 1 nm to 2 nm) is uniformly controlled.
- a carbon nanotube manufacturing method in which a carbon source and a non-oxidizing gas are supplied to a cylindrical chamber to generate carbon nanotubes.
- the chamber is provided in a partial range in the cylinder axis direction of the chamber, and is heated to a temperature at which carbon nanotubes are generated, downstream of the reaction zone, and in the chamber
- a deposition zone that is provided upstream of a gas vent for exhausting gas, cools and deposits the generated carbon nanotubes, and a deposition state detection unit that detects a physical property value indicating a deposition state of the carbon nanotubes in the deposition zone; , Is provided.
- the control valve of the exhaust pipe connected to the gas vent is closed to deposit the carbon nanotubes in the deposition zone (deposition) Step); and Opening the control valve and recovering the carbon nanotubes deposited in the deposition zone when the physical property value exceeds a predetermined threshold (recovery step); Is included.
- a recovery unit is disposed below the chamber.
- the carbon nanotubes deposited in the deposition zone may be dropped onto the collection unit.
- the physical property value indicating the deposition state of the carbon nanotube is the pressure in the chamber.
- FIG. 1 is a schematic diagram illustrating an example of a CNT manufacturing apparatus according to an embodiment.
- FIG. 2 is a control flow diagram of the CNT manufacturing apparatus according to one embodiment.
- a CNT manufacturing apparatus 1 is a CNT manufacturing apparatus that generates CNTs in a flowing gas phase.
- the apparatus 1 includes a cylindrical chamber 10, a carbon source supply unit 30 that supplies a carbon source A to the chamber 10 from a carbon source supply port 32 that opens to the chamber 10, and a gas supply port 82 that opens to the chamber 10.
- the control part 90 electrically connected is provided.
- the carbon source supply unit 30 is configured to supply (for example, spray) the carbon source A to the chamber 10 from a carbon source supply port 32 that opens to the chamber 10.
- the carbon source supply unit 30 includes a carbon source introduction pipe 34 that extends in a reaction zone 20 (described later) in the chamber 10 and continues to the carbon source supply port 32.
- a carbon source supply port 32 provided at the tip of the carbon source introduction pipe 34 opens at or near the reaction zone 20.
- a carbon source supply port 32 provided at the tip of the carbon source introduction pipe 34 opens to the upstream side of the chamber 10.
- the carbon source A is directly supplied to the reaction zone 20 (high temperature region), whereby the carbon source (typically liquid) A supplied from the carbon source supply port 32 is gasified in a short time. (Vaporization) can generate CNTs from the carbon source A more efficiently. Further, by using the carbon source introduction pipe 34, the heat of the reaction zone 20 is transmitted from the carbon source supply port 32 through the wall surface of the carbon source introduction pipe 34 to the carbon source (liquid) A in the introduction pipe 34, thereby The carbon source A supplied from the source supply port 32 can be gasified in a short time.
- the carbon source (typically liquid) A supplied from the carbon source supply port 32 is gasified in a short time.
- various carbon (C) -containing materials capable of generating CNTs by a CVD method can be used.
- a carbon source that takes the form of a liquid at room temperature (25 ° C.) is preferred.
- aromatic hydrocarbons such as toluene, benzene, xylene, naphthalene, anthracene, and tetralin; acyclic saturated fats such as hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, and heptadecane
- a hydrocarbon group, a cyclic saturated aliphatic hydrocarbon such as decalin, cyclohexane, hexane, and tetradecahydrophenanthrene; a mixture thereof; and the like can be used as a carbon source.
- carbon source with a high carbon content
- toluene, benzene or the like can be preferably used as the carbon source.
- These carbon sources are preferable in that they can be gasified (vaporized) in a short time after being supplied from the carbon source supply port 32 to the reaction zone 20 of the chamber 10.
- the carbon source supply unit 30 can supply the catalyst metal or the catalyst metal compound together with the carbon source described above to the chamber 10 from the carbon source supply port 32.
- the 1 type, or 2 or more types of metal which can catalyze the thermal decomposition of a carbon source (for example, toluene) in CVD method can be used.
- a carbon source for example, toluene
- iron (Fe), cobalt (Co), nickel (Ni), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), molybdenum (Mo), ruthenium (Ru) ), Copper (Cu), or the like can be used as the catalyst metal. It is preferable to use at least one of Fe and Co. This gives a better quality product.
- catalytic metal compounds include organic transition metal compounds and inorganic transition metal compounds.
- organic transition metal compound include ferrocene, nickelocene, cobaltocene, iron carbonyl, iron acetylacetonate, and iron oleate. Of these, ferrocene is preferably used.
- the carbon source supply unit 30 can supply a sulfur compound together with the carbon source and the catalyst metal described above to the chamber 10 from the carbon source supply port 32.
- sulfur compounds include organic sulfur compounds and inorganic sulfur compounds.
- the organic sulfur compound include sulfur-containing heterocyclic compounds such as thiophene, thianaphthene, and benzothiophene.
- an inorganic sulfur compound hydrogen sulfide etc. are illustrated, for example. Of these, thiophene is preferably used. Thereby, the production
- the gas supply unit 80 is configured to supply a non-oxidizing gas (carrier gas) to the chamber 10 from a gas supply port 82 opened to the chamber 10.
- the gas supply unit 80 includes a gas supply pipe 84 that extends through the reaction zone 20 and communicates with the gas supply port 82.
- a gas supply port 82 provided at the tip of the gas supply pipe 84 is open at or near the reaction zone 20.
- a gas supply port 82 provided at the distal end of the gas supply pipe 84 opens to the upstream side of the chamber 10.
- the carrier gas supplied to the chamber 10 from the gas supply port 82 it is appropriate to use a non-oxidizing gas.
- a non-oxidizing gas it is preferable to use one or more selected from a reducing gas and an inert gas as the carrier gas.
- the reducing gas include hydrogen (H 2 ) gas, ammonia (NH 3 ) gas, and the like.
- the inert gas include argon (Ar) gas, nitrogen (N 2 ) gas, helium (He) gas, and the like.
- a reducing gas for example, H 2 gas
- H 2 gas is used as the carrier gas.
- the non-oxidizing gas supplied from the gas supply port 82 to the chamber 10 may include a carbon source gas that is gaseous at normal temperature.
- a carbon source gas a material that is thermally decomposed at a temperature lower than that of the carbon source supplied from the carbon source supply port 32 to the chamber 10 is preferable.
- the carbon source gas having such properties include unsaturated aliphatic hydrocarbons such as ethylene having a double bond, propylene, and acetylene having a triple bond. A mixture of these may be used as the carbon source gas.
- the gas supply unit 80 and the carbon source supply unit 30 have a double tube structure in which the gas supply pipe 84 is an outer pipe and the carbon source introduction pipe 34 is an inner pipe.
- the gas supply port 82 provided at the tip of the gas supply pipe 84 and the carbon source supply port 32 provided at the tip of the carbon source introduction pipe 34 are arranged concentrically.
- the carbon source supply port 32 provided at the tip of the carbon source introduction pipe 34 protrudes downstream (downward) from the gas supply port 82 provided at the tip of the gas supply pipe 84.
- Such a configuration is advantageous for gasifying and diffusing the carbon source liquid supplied from the carbon source supply port 32 when a liquid material at room temperature is used as the carbon source.
- the non-oxidizing gas supplied from the gas supply port 82 is supplied from the carbon source supply port 32 by adopting a double tube structure in which the gas supply tube 84 is an outer tube and the carbon source introduction tube 34 is an inner tube.
- the supplied carbon source (liquid) promotes gasification and diffusion of the carbon source (liquid).
- the gasified carbon source can be better dispersed in the reaction zone 20. Therefore, higher quality CNT can be generated efficiently (for example, in high yield).
- the exhaust pipe 50 is configured to be able to exhaust the gas in the chamber 10 from a gas vent 52 disposed downstream of the deposition zone 22 described later of the chamber 10.
- a gas vent 52 of the exhaust pipe 50 is opened on a side surface of a recovery unit (collection container) 70 which will be described later connected to the downstream side (downward) of the chamber 10.
- a control valve 60 is provided in the middle of the exhaust pipe 50.
- This control valve (for example, electromagnetic valve) 60 is electrically connected to the control unit 90 and is configured to be opened and closed under the control of the control unit 90.
- the control valve 60 is controlled to be closed during normal use (that is, during the production of CNTs).
- the exhaust pipe 50 includes a bypass pipe 54 that does not pass through the control valve 60. Thereby, even when the control valve 60 is closed, a certain amount of gas is discharged from the gas vent 52 through the bypass pipe 54.
- the amount of non-oxidizing gas (carrier gas) supplied from the gas supply port 82 to the chamber 10 and the gas discharged from the gas vent 52 through the bypass pipe 54 with the control valve 60 closed (
- the carrier gas may contain a reaction gas generated by thermal decomposition of the carbon source, an unreacted carbon source, etc.). It is possible to control the movement of the gasified carbon source so that it does not diffuse upstream and downstream (in other words, the gasified carbon source remains in the reaction zone 20).
- the chamber 10 is typically formed in a straight tube shape (that is, so that the axis extends linearly), and the cross-sectional shape thereof is a round shape such as a circle, an ellipse, an oval, an oval, or the like. It is preferable that Alternatively, the cross-sectional shape may be a polygonal shape (preferably a hexagon or more, such as a hexagon to an icosahedron).
- the inner diameter and length of the chamber 10 can be appropriately set in consideration of the desired CNT production capacity, equipment cost, and the like.
- the CNT manufacturing apparatus disclosed herein can be preferably implemented, for example, in a mode using a cylinder having an inner diameter of about 50 mm to 500 mm.
- the inner diameter of the chamber 10 is preferably about 50 mm to 200 mm.
- the length of the chamber 10 can be about 1 time or more (typically about 1 to 10 times) of the inner diameter.
- the length of the chamber 10 in the apparatus 1 of this embodiment is about 1400 mm, of which the length of the reaction zone 20 is about 800 mm and the length of the deposition zone 22 is about 400 mm.
- a material having heat resistance corresponding to the CNT generation temperature and high chemical stability can be appropriately employed.
- a particularly preferable material is ceramics.
- the opening on the upstream side of the chamber 10 is closed by the upstream lid 12. On the other hand, the downstream end of the chamber 10 is open.
- the reaction zone 20 is a zone heated to a temperature at which CNTs are generated in the chamber 10.
- a partial range (here, an upper portion and a central portion) of the chamber 10 in the cylinder axis direction is surrounded by the heater 3, and a portion located inside the enclosed region is the reaction zone 20.
- the heater 3 only needs to be able to heat the reaction zone 20 to a temperature suitable for the production of CNT (typically about 500 to 2000 ° C., preferably about 1000 to 1600 ° C., for example, about 1100 to 1200 ° C.).
- the shape and heating method are not particularly limited.
- An example of the heater 3 that can be preferably used is an electric furnace.
- two electric furnaces having a substantially semicircular cross-sectional shape are used as the heater 3, and these electric furnaces face each other so as to surround a partial range of the chamber 10.
- the carbon source supplied from the carbon source supply port 32 is gasified (vapor) and further thermally decomposed to generate CNTs.
- the deposition zone 22 is provided in the chamber 10 downstream of the reaction zone 20 and cools and deposits the generated CNTs 24. That is, the CNTs 24 generated by pyrolyzing the carbon source in the reaction zone 20 move to the deposition zone 22 and are cooled, and are typically deposited near the outlet of the chamber 10. Accordingly, the vicinity of the outlet of the chamber 10 is gradually covered with CNTs 24.
- a cooling mechanism for example, a water cooling jacket
- for forcibly cooling the deposition zone 22 may be disposed around the deposition zone 22. In this way, the CNTs 24 can be efficiently deposited in the deposition zone 22.
- the CNT deposited in the deposition zone 22 can be collected by switching the control valve (electromagnetic valve) 60 described above to an open state. That is, when the control valve 60 is switched to the open state, a large amount of high-pressure gas (gasified carbon source and non-oxidizing gas) accumulated in the reaction zone 20 passes through the deposition zone 22 and the recovery unit 70 described later, and the gas vent 52. Discharged from.
- the CNT accumulated in the deposition zone 22 can be moved to the collection unit 70 by the gas flow and collected by the collection unit 70.
- the accumulation state detection unit 40 is configured to detect a physical property value indicating the accumulation state of CNTs in the accumulation zone 22.
- the accumulation state detection unit 40 is not particularly limited as long as it can detect a physical property value indicating the accumulation state of CNTs.
- the accumulation state detection unit 40 is a pressure sensor 40. That is, when the deposition zone 22 is thickly covered with CNT and approaches a closed state, the gasified carbon source and the non-oxidizing gas remain in the reaction zone 20, so that the pressure in the chamber 10 increases. Therefore, by measuring the pressure in the chamber 10, it is possible to grasp the state of CNT deposition in the deposition zone 22.
- the pressure sensor 40 may be disposed upstream of the deposition zone 22. In this embodiment, the pressure sensor 40 is attached to the lower surface of the upstream lid 12 that closes the upstream side of the chamber 10.
- the apparatus 1 includes a recovery unit 70 that recovers CNTs sent from the deposition zone 22 to the downstream side when the control valve 60 is switched to an open state.
- the recovery unit 70 is disposed downstream of the deposition zone 22 and upstream of the gas vent 52. In this way, CNTs can be efficiently recovered while the exhaust gas moves from the deposition zone 22 to the gas vent 52.
- the collection unit 70 is a collection container 70. A gas vent 52 is opened on the side surface of the collection container 70. Further, the recovery container 70 is connected to the downstream end of the chamber 10 with the upper side opened. In other words, the recovery container 70 is disposed below the deposition zone 22 with the top opened.
- the collection unit 70 may include a capturing mechanism such as mesh steel so that the CNT can be easily collected.
- Control unit 90 controls the control valve 60. It is configured to close and deposit CNTs in the deposition zone 22.
- the control valve 60 is opened to move the CNT deposited in the deposition zone 22 to the collection unit 70, and the collection unit 70 It is configured to collect.
- the typical configuration of the control unit 90 includes at least a ROM (Read Only Memory) storing a program for performing such control, a CPU (Central Processing Unit) capable of executing the program, and temporary data.
- a RAM random access memory
- an input / output port (not shown) are included.
- Various signals (output) from the above-described accumulation state detection unit (pressure sensor) 40 and the like are input to the control unit 90 via an input port. Further, the control unit 90 outputs an opening / closing drive signal to the control valve 60 through an output port.
- the ROM stores a threshold value of pressure that is a criterion for opening / closing the control valve.
- FIG. 2 is a flowchart illustrating an example of a control valve opening / closing control processing routine executed by the CPU of the control unit 90 according to the present embodiment. This opening / closing control processing routine is repeatedly executed every predetermined time immediately after the apparatus 1 is operated.
- the control unit 90 first reads a signal input from the pressure sensor 40 and measures the pressure in the chamber 10 in step S10. Next, in step S20, it is determined whether or not the measured pressure value measured by the pressure sensor 40 exceeds a predetermined threshold value. When the measurement value of the pressure measured by the pressure sensor 40 does not exceed the predetermined threshold value (in the case of “NO”), the control unit 90 determines that it is not the timing to collect the CNT deposited in the deposition zone 22, Proceeding to step S30, the control valve 60 is closed. As a result, CNTs are deposited in the deposition zone 22. In the state in which CNTs are deposited in the deposition zone 22, the gasified carbon source stays better in the reaction zone 20, so that high-quality CNTs can be generated efficiently.
- step S40 the control valve 60 is opened.
- the CNT deposited in the deposition zone 22 moves downstream along with the gas flow and is collected by the collection unit 70. In this way, the CNT deposited in the deposition zone 22 can be collected at an appropriate timing. Thereafter, the process returns to the start again, and thereafter, the operations in steps S10 to S40 are repeated.
- the control valve 60 is closed to deposit CNTs in the deposition zone 22 (typically, adhere to the inner wall of the chamber), so that the carbon source in the reaction zone 20 upstream from the deposition zone 22 is obtained. (That is, diffusion to the downstream side of the reaction zone 20 is suppressed), and high-quality CNTs can be efficiently generated (for example, in high yield) from the carbon source. Further, when the deposition of CNTs progresses to some extent in the deposition zone 22, the CNTs can be continuously produced by opening the control valve 60 and collecting the CNTs deposited in the deposition zone 22. That is, the apparatus 1 having the above configuration is suitable for continuous production of CNTs.
- a carbon nanotube manufacturing method in which a carbon source and a non-oxidizing gas are supplied to a cylindrical chamber 10 to generate carbon nanotubes.
- the chamber 10 is provided in a partial range in the cylinder axis direction of the chamber 10 and is heated to a temperature at which carbon nanotubes are generated, downstream of the reaction zone 20, and
- the deposition zone 22 is provided upstream of the gas vent 52 for discharging the gas in the chamber 10 and cools and deposits the generated carbon nanotubes, and the physical properties indicating the deposition state of the carbon nanotubes in the deposition zone 22 are shown.
- a deposition state detection unit 40 for detection.
- the control valve 60 of the exhaust pipe 50 connected to the gas vent 52 is closed, and the carbon nanotube is placed in the deposition zone 22.
- Depositing depositing
- the control valve 60 is opened to collect the carbon nanotubes deposited in the deposition zone 22 (recovery step); Is included. According to such a method, it is possible to obtain high-quality CNTs continuously and efficiently (for example, at a high yield) by repeatedly performing the deposition step and the recovery step.
- the physical property value indicating the CNT deposition state in the deposition zone 22 of the chamber 10 is the CNT deposition amount calculated from the image of the deposition zone 22 imaged by the imaging device 40. 1 is different.
- the imaging device 40 is used to directly grasp the CNT accumulation state.
- the imaging device 40 can be used without particular limitation as long as it can capture the periphery of the deposition zone 22 with high resolution from the outside of the chamber 10.
- a known imaging device using a CCD image sensor or a CMOS image sensor can be used.
- the imaging device 40 captures the CNT accumulation state in the deposition zone 22 in the process of manufacturing the CNT as imaging data, and transmits this imaging data to the control unit 90.
- the imaging device 40 is installed in a direction orthogonal to the CNT deposition direction (the radial direction of the chamber 10) (for example, the imaging device 40 is installed on the upstream lid 12 of the chamber 10 and directed downward from the location). It is configured to image the deposition zone 22. In this way, it is possible to image the deposition state of the CNT deposited in the deposition zone 22 more accurately.
- the imaging device 40 is configured to continuously (time-dependently) image the deposition zone 22 in the process of producing CNTs.
- the imaging device 40 continuously captures the accumulation state of CNTs in the deposition zone 22 as imaging data (sequentially), and transmits this imaging data to the control unit 90 continuously (sequentially).
- the term “continuously” as used herein includes not only a mode in which imaging is performed without interruption, but also that imaging is performed continuously at regular intervals.
- the deposition state of the CNT deposited in the deposition zone 22 can be grasped more directly and accurately. Therefore, the CNT deposited in the deposition zone 22 can be collected at an appropriate timing.
- the physical property value indicating the CNT deposition state in the deposition zone 22 of the chamber 10 is calculated from the pressure in the chamber 10 measured by the pressure sensor or the image of the deposition zone 22 captured by the imaging device. An example of the amount of accumulated CNT was shown.
- the physical property value indicating the deposition state of CNT in the deposition zone 22 is not limited to this.
- the CNT deposition state may be grasped by a physical property value such as the temperature in the chamber 10.
- the recovery container 70 is provided below the chamber 10, but the recovery container 70 may be omitted.
- the material of the chamber 10 constituting the CNT manufacturing apparatus 1 is not limited to ceramics as in the above embodiment, and it goes without saying that it can be changed as appropriate.
- specific configurations such as the shape of the chamber 10, the carbon source introduction pipe 34, the gas supply pipe 84, the heater 3, and the recovery container 70 can be arbitrarily changed within the intended scope of the present invention. .
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Abstract
Description
なお、本国際出願は2015年10月1日に出願された日本国特許出願第2015-196221号に基づく優先権を主張しており、その出願の全内容は本明細書中に参照として組み入れられている。
その方法において、前記チャンバには、当該チャンバの筒軸方向の一部範囲に設けられ、カーボンナノチューブが生成する温度に加熱される反応ゾーンと、当該反応ゾーンよりも下流で、かつ、チャンバ内のガスを排出するガス抜き口よりも上流に設けられ、前記生成したカーボンナノチューブを冷却して堆積する堆積ゾーンと、当該堆積ゾーンにおけるカーボンナノチューブの堆積状態を示す物性値を検知する堆積状態検知部と、が設けられている。
ここで、以下の工程:
前記堆積ゾーンにおけるカーボンナノチューブの堆積状態を示す物性値が所定の閾値以下の場合に、前記ガス抜き口に連結された排気管の制御バルブを閉じて前記堆積ゾーンにカーボンナノチューブを堆積すること(堆積工程);および、
当該物性値が所定の閾値を超えた場合に、前記制御バルブを開いて前記堆積ゾーンに堆積されたカーボンナノチューブを回収すること(回収工程);
を包含する。
かかる方法によると、上記堆積工程と上記回収工程とを繰り返し行うことで、高品質なCNTを連続して効率よく(例えば高収率で)得ることができる。
ここに開示されるCNT製造装置の好ましい一形態につき、図面を参照しつつ説明する。図1に示すように、本実施形態に係るCNT製造装置1は、CNTを流動する気相中で生成させるCNT製造装置である。この装置1は、筒体のチャンバ10と、チャンバ10に開口する炭素源供給口32から該チャンバ10に炭素源Aを供給する炭素源供給部30と、チャンバ10に開口するガス供給口82から該チャンバ10に非酸化性ガスを供給するガス供給部80と、チャンバ10内のガスを排出可能に構成された排気管50と、排気管50に設けられた制御バルブ60と、制御バルブ60に電気的に接続された制御部90とを備えている。
炭素源供給部30は、チャンバ10に開口する炭素源供給口32から該チャンバ10に炭素源Aを供給(例えば噴霧)するものとして構成されている。この実施形態では、炭素源供給部30は、チャンバ10内の後述する反応ゾーン20内を延びて炭素源供給口32に連なる炭素源導入管34を備えている。炭素源導入管34の先端に設けられた炭素源供給口32は、反応ゾーン20またはその近傍に開口している。炭素源導入管34の先端に設けられた炭素源供給口32は、チャンバ10の上流側に開口している。このように炭素源Aが、反応ゾーン20(高温領域)に直接供給される構成とすることにより、炭素源供給口32から供給された炭素源(典型的には液体)Aを短時間でガス(蒸気)化して該炭素源AからCNTをより効率よく生成させることができる。また、炭素源導入管34を用いることで、炭素源供給口32から炭素源導入管34の壁面を通じて反応ゾーン20の熱を該導入管34内の炭素源(液体)Aに伝え、これにより炭素源供給口32から供給された炭素源Aを短時間でガス化することができる。
ガス供給部80は、チャンバ10に開口するガス供給口82から該チャンバ10に非酸化性ガス(キャリアガス)を供給するものとして構成されている。この実施形態では、ガス供給部80は、反応ゾーン20内を延びてガス供給口82に連なるガス供給管84を備えている。ガス供給管84の先端に設けられたガス供給口82は、反応ゾーン20またはその近傍に開口している。ガス供給管84の先端に設けられたガス供給口82は、チャンバ10の上流側に開口している。
排気管50は、チャンバ10の後述する堆積ゾーン22よりも下流に配置されたガス抜き口52からチャンバ10内のガスを排出可能に構成されている。この実施形態では、チャンバ10の下流側(下方)に連結された後述する回収部(回収容器)70の側面に排気管50のガス抜き口52が開口している。また、排気管50の途上には、制御バルブ60が設けられている。この制御バルブ(例えば電磁バルブ)60は、制御部90に電気的に接続され、制御部90の制御により開閉自在に構成されている。制御バルブ60は、通常の使用時(すなわちCNTの製造時)においては閉状態に制御されている。そして、後述するCNTを回収する際に、閉状態から開状態に切り替えられる。また、この実施形態では、排気管50は、制御バルブ60を経由しないバイパス管54を備えている。これにより、制御バルブ60が閉状態であっても、バイパス管54を通じてガス抜き口52から一定量のガスが排出されるようになっている。好ましい一態様では、ガス供給口82からチャンバ10に供給される非酸化性ガス(キャリアガス)の量と、制御バルブ60を閉じた状態においてガス抜き口52からバイパス管54を通じて排出されるガス(上記キャリアガスのほか、炭素源の熱分解により生じた反応ガスや未反応の炭素源等を含み得る。)の量とのバランスを適切に設定することにより、ガス化した炭素源が反応ゾーン20よりも上流側および下流側に拡散しないように(換言すれば、ガス化した炭素源を反応ゾーン20内に留めるように)ガス化した炭素源の移動をコントロールすることができる。
チャンバ10は、典型的には直管状に(すなわち、軸が直線状に延びるように)形成されており、その断面形状は、円形、楕円形、卵型、長円形等の丸みを帯びた形状であることが好ましい。あるいは、上記断面形状が多角(好ましくは六角以上、例えば六角~二十角)形状であってもよい。チャンバ10の内径および長さは、所望するCNT生産能力や設備コスト等を考慮して適宜設定することができる。CNTを効率よく生成させるという観点から、ここに開示されるCNT製造装置は、例えば、内径が凡そ50mm~500mmの筒体を用いる態様で好ましく実施することができる。通常は、チャンバ10の内径を凡そ50mm~200mmとすることが好ましい。チャンバ10の長さは、内径の凡そ1倍以上(典型的には1~10倍程度)の長さとすることができる。本実施形態の装置1におけるチャンバ10の長さは約1400mmであり、そのうち反応ゾーン20の長さは約800mm、堆積ゾーン22の長さは約400mmである。チャンバ10の構成材質としては、上記CNT生成温度に見合った耐熱性を有し且つ化学的安定性の高いものを適宜採用することができる。特に好ましい材質としてセラミックスが挙げられる。チャンバ10の上流側の開口は、上流蓋12によって塞がれている。一方、チャンバ10の下流端は開口状態となっている
反応ゾーン20は、チャンバ10内においてCNTが生成する温度に加熱されるゾーンである。この実施形態では、チャンバ10の筒軸方向の一部範囲(ここでは上部および中央部)はヒータ3によって囲まれており、この囲まれた領域の内側に位置する部分が反応ゾーン20となっている。ヒータ3は、反応ゾーン20をCNTの生成に適した温度(典型的には凡そ500~2000℃、好ましくは凡そ1000~1600℃、例えば凡そ1100~1200℃)に加熱可能であればよく、その形状や加熱方式は特に限定されない。好ましく使用し得るヒータ3の一例として電気炉が挙げられる。本実施形態では、ヒータ3として断面形状が略半円形の二つの電気炉を使用し、それらの電気炉を向かい合わせてチャンバ10の一部範囲を囲むように構成されている。反応ゾーン20をCNTが生成する温度に加熱することにより、炭素源供給口32から供給された炭素源がガス(蒸気)化、さらに熱分解されてCNTが生成する。
堆積ゾーン22は、チャンバ10内において反応ゾーン20よりも下流に設けられ、生成したCNT24を冷却して堆積するゾーンである。すなわち、反応ゾーン20で炭素源を熱分解することにより生成したCNT24は、堆積ゾーン22に移動して冷却され、典型的にはチャンバ10の出口付近に堆積する。これに伴ってチャンバ10の出口付近がCNT24によって次第に厚く覆われる。堆積ゾーン22を強制的に冷却するための冷却機構(例えば水冷ジャケット)を堆積ゾーン22の周囲に配置してもよい。このようにすれば、堆積ゾーン22にCNT24を効率良く堆積することができる。このように、反応ゾーン20よりも下流の堆積ゾーン22をCNTによって厚く覆う(ひいては閉塞状態に近づける)ことにより、ガス化した炭素源が反応ゾーン20内に留まりやすくなる(すなわち、反応ゾーン20の下流側への拡散が抑えられる)。このことより、該炭素源から高品質なCNTをより効率よく(例えば高収率で)生成させることができる。また、堆積ゾーン22に堆積したCNTは、前述した制御バルブ(電磁バルブ)60を開状態に切り替えることで、回収することが可能である。すなわち、制御バルブ60を開状態に切り替えると、反応ゾーン20に溜まった大量の高圧ガス(ガス化した炭素源および非酸化性ガス)が堆積ゾーン22および後述する回収部70を経てガス抜き口52から排出される。このガス流れに乗って、堆積ゾーン22に堆積されたCNTを回収部70まで移動させ、回収部70にて回収することができる。
堆積状態検知部40は、堆積ゾーン22におけるCNTの堆積状態を示す物性値を検知するものとして構成されている。堆積状態検知部40は、CNTの堆積状態を示す物性値を検知し得るものであれば特に制限されない。この実施形態では、堆積状態検知部40は、圧力センサ40である。すなわち、堆積ゾーン22がCNTで厚く覆われて閉塞状態に近づくと、ガス化した炭素源および非酸化性ガスが反応ゾーン20内に留まるため、チャンバ10内の圧力が上昇する。したがって、チャンバ10内の圧力を計測することにより、堆積ゾーン22でのCNTの堆積状態を把握することができる。圧力センサ40は、堆積ゾーン22よりも上流側に配置されていればよい。この実施形態では、圧力センサ40は、チャンバ10の上流側を塞ぐ上流蓋12の下面に取り付けられている。
本実施形態に係る装置1は、制御バルブ60を開状態に切り替えた際に、堆積ゾーン22から下流側へと送られてきたCNTを回収する回収部70を備えている。回収部70は、堆積ゾーン22より下流で、かつ、ガス抜き口52よりも上流に配置されている。このようにすれば、排ガスが堆積ゾーン22からガス抜き口52へ移動する間にCNTを効率良く回収することができる。この実施形態では、回収部70は回収容器70である。回収容器70の側面にはガス抜き口52が開口している。また、回収容器70は、上方が開口した状態で、チャンバ10の下流端に連結されている。すなわち、回収容器70は、上方が開口した状態で、堆積ゾーン22の下方に配置されている。そして、制御バルブ60を開状態に切り替えた際に、堆積ゾーン22に堆積したCNTを回収容器70に落下させるように構成されている。このように、CNTを自重で落下させることで、CNTをより効率良く回収することができる。回収部70は、CNTを回収しやすいようにメッシュ鋼等の捕捉機構を備えていてもよい。
制御部90は、堆積状態検知部(この例では圧力センサ)40で検知したCNTの堆積状態を示す物性値(ここではチャンバ10の内圧)が所定の閾値以下の場合には、制御バルブ60を閉じて堆積ゾーン22にCNTを堆積するように構成されている。また、当該CNTの堆積状態を示す物性値が所定の閾値を超えた場合には、制御バルブ60を開いて堆積ゾーン22に堆積されたCNTを回収部70まで移動させ、該回収部70にて回収するように構成されている。制御部90の典型的な構成には、少なくとも、かかる制御を行うためのプログラムを記憶したROM(Read Only Memory)と、そのプログラムを実行可能なCPU(Central Processing Unit)と、一時的にデータを記憶するRAM(random access memory)と、図示しない入出力ポートとが含まれる。該制御部90には、前述した堆積状態検知部(圧力センサ)40などからの各種信号(出力)などが入力ポートを介して入力される。また、該制御部90からは、制御バルブ60への開閉駆動信号などが出力ポートを介して出力される。ROMには、制御バルブの開閉の判断基準になる圧力の閾値などが記憶されている。
その方法において、前記チャンバ10には、当該チャンバ10の筒軸方向の一部範囲に設けられ、カーボンナノチューブが生成する温度に加熱される反応ゾーン20と、当該反応ゾーン20よりも下流で、かつ、チャンバ10内のガスを排出するガス抜き口52よりも上流に設けられ、生成したカーボンナノチューブを冷却して堆積する堆積ゾーン22と、当該堆積ゾーン22におけるカーボンナノチューブの堆積状態を示す物性値を検知する堆積状態検知部40と、が設けられている。
ここで、以下の工程:
前記堆積ゾーン22におけるカーボンナノチューブの堆積状態を示す物性値が所定の閾値以下の場合に、前記ガス抜き口52に連結された排気管50の制御バルブ60を閉じて前記堆積ゾーン22にカーボンナノチューブを堆積すること(堆積工程);および、
当該物性値が所定の閾値を超えた場合に、前記制御バルブ60を開いて前記堆積ゾーン22に堆積されたカーボンナノチューブを回収すること(回収工程);
を包含する。
かかる方法によると、上記堆積工程と上記回収工程とを繰り返し行うことで、高品質なCNTを連続して効率よく(例えば高収率で)得ることができる。
以上、本発明の一実施形態にかかるCNT製造装置1において実行される制御バルブの開閉制御について説明した。次に、本発明の他の一実施形態にかかるCNT製造装置1によって実行可能な制御バルブの開閉制御について説明する。
Claims (11)
- カーボンナノチューブを生成させるカーボンナノチューブ製造装置であって、
筒体のチャンバと、
前記チャンバに開口する炭素源供給口から該チャンバに炭素源を供給する炭素源供給部と、
前記チャンバに開口するガス供給口から該チャンバに非酸化性ガスを供給するガス供給部と、
前記チャンバ内のガスをガス抜き口から排出可能に構成された排気管と、
前記排気管に設けられた制御バルブと
を備え、
前記チャンバは、
当該チャンバの筒軸方向の一部範囲に設けられ、カーボンナノチューブが生成する温度に加熱される反応ゾーンと、
前記反応ゾーンよりも下流で、かつ、前記ガス抜き口よりも上流に設けられ、前記生成したカーボンナノチューブを冷却して堆積する堆積ゾーンと、
前記堆積ゾーンにおけるカーボンナノチューブの堆積状態を示す物性値を検知する堆積状態検知部と
を備え、
ここで、前記堆積状態検知部で検知したカーボンナノチューブの堆積状態を示す物性値が所定の閾値以下の場合には、前記制御バルブを閉じて前記堆積ゾーンにカーボンナノチューブを堆積するように構成され、
当該物性値が所定の閾値を超えた場合には、前記制御バルブを開いて前記堆積ゾーンに堆積されたカーボンナノチューブを回収するように構成されている、カーボンナノチューブ製造装置。 - 前記カーボンナノチューブを回収する回収部をさらに備え、
前記回収部は、前記堆積ゾーンより下流で、かつ、前記ガス抜き口よりも上流に配置されている、請求項1に記載の装置。 - 前記回収部は、前記チャンバの下方に配置され、
前記堆積ゾーンに堆積されたカーボンナノチューブを前記回収部に落下させるように構成されている、請求項2に記載の装置。 - 前記カーボンナノチューブの堆積状態を示す物性値は、前記チャンバ内の圧力である、請求項1~3の何れか一つに記載の装置。
- 前記炭素源供給口は、前記反応ゾーンまたはその近傍に配置されている、請求項1~4の何れか一つに記載の装置。
- 前記炭素源供給部は、前記反応ゾーン内を延びて前記炭素源供給口に連なる炭素源導入管を備える、請求項5に記載の装置。
- 前記ガス供給部は、前記反応ゾーン内を延びて前記ガス供給口に連なるガス供給管を備え、
前記ガス供給管および前記炭素源導入管は、当該ガス供給管を外管とし、当該炭素源導入管を内管とする二重管構造を有する、請求項6に記載の装置。 - 前記ガス供給部は、前記ガス供給口から前記チャンバに非酸化性ガスとともに炭素源ガスを供給するように構成されている、請求項1~7の何れか一つに記載の装置。
- 筒体のチャンバに炭素源および非酸化性ガスを供給してカーボンナノチューブを生成させるカーボンナノチューブの製造方法であって、
前記チャンバには、当該チャンバの筒軸方向の一部範囲に設けられ、カーボンナノチューブが生成する温度に加熱される反応ゾーンと、当該反応ゾーンよりも下流で、かつ、チャンバ内のガスを排出するガス抜き口よりも上流に設けられ、前記生成したカーボンナノチューブを冷却して堆積する堆積ゾーンと、当該堆積ゾーンにおけるカーボンナノチューブの堆積状態を示す物性値を検知する堆積状態検知部とが設けられており、
ここで、以下の工程:
前記堆積ゾーンにおけるカーボンナノチューブの堆積状態を示す物性値が所定の閾値以下の場合に、前記ガス抜き口に連結された排気管の制御バルブを閉じて前記堆積ゾーンにカーボンナノチューブを堆積すること;および、
当該物性値が所定の閾値を超えた場合に、前記制御バルブを開いて前記堆積ゾーンに堆積されたカーボンナノチューブを回収すること;
を包含する、カーボンナノチューブ製造方法。 - 前記チャンバの下方には、回収部が配置されており、
前記カーボンナノチューブを回収する工程では、前記堆積ゾーンに堆積されたカーボンナノチューブを前記回収部に落下させる、請求項9に記載の製造方法。 - 前記カーボンナノチューブの堆積状態を示す物性値は、前記チャンバ内の圧力である、請求項9または10に記載の製造方法。
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- 2016-09-30 US US15/765,003 patent/US20180264443A1/en not_active Abandoned
- 2016-09-30 KR KR1020187011923A patent/KR102672047B1/ko active IP Right Grant
- 2016-09-30 CN CN201680058037.7A patent/CN108349728B/zh active Active
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2019
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US20180264443A1 (en) | 2018-09-20 |
JP6479202B2 (ja) | 2019-03-06 |
CN108349728A (zh) | 2018-07-31 |
KR102672047B1 (ko) | 2024-06-05 |
US20220372625A1 (en) | 2022-11-24 |
KR20180064437A (ko) | 2018-06-14 |
JP6786638B2 (ja) | 2020-11-18 |
JPWO2017057751A1 (ja) | 2018-08-09 |
CN108349728B (zh) | 2021-12-24 |
JP2019064918A (ja) | 2019-04-25 |
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