WO2020085170A1 - Procédé et appareil de production d'un corps adhéré à un catalyseur, et procédé et appareil de production de nanostructure de carbone fibreux - Google Patents

Procédé et appareil de production d'un corps adhéré à un catalyseur, et procédé et appareil de production de nanostructure de carbone fibreux Download PDF

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Publication number
WO2020085170A1
WO2020085170A1 PCT/JP2019/040739 JP2019040739W WO2020085170A1 WO 2020085170 A1 WO2020085170 A1 WO 2020085170A1 JP 2019040739 W JP2019040739 W JP 2019040739W WO 2020085170 A1 WO2020085170 A1 WO 2020085170A1
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Prior art keywords
catalyst
supply port
raw material
vertical container
producing
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PCT/JP2019/040739
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English (en)
Japanese (ja)
Inventor
墨宸 李
野田　優
里沙 前田
利男 大沢
明慶 渋谷
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学校法人早稲田大学
日本ゼオン株式会社
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Priority to JP2020553253A priority Critical patent/JP7548504B2/ja
Publication of WO2020085170A1 publication Critical patent/WO2020085170A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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 manufacturing method and a manufacturing apparatus for a catalyst-adhered body, and a manufacturing method and a manufacturing apparatus for a fibrous carbon nanostructure.
  • the present invention provides a method for producing a catalyst adhering body that can be suitably used for synthesizing a fibrous carbon nanostructure, and a catalyst adhering body producing apparatus that can suitably carry out the method for producing such a catalyst adhering body.
  • the present invention is capable of suitably carrying out the method for producing a fibrous carbon nanostructure using the above-mentioned catalyst-adhered body, and the method for producing such a fibrous carbon nanostructure.
  • the present invention relates to a body manufacturing device.
  • Patent Documents 1 and 2 describe a method for producing a catalyst for vapor phase oxidation.
  • Patent Documents 1 and 2 there is a method of producing a supported catalyst in which a catalyst component is attached to the surface of carrier particles by spraying a suspension containing a catalytically active material onto fluidized carrier particles.
  • CNT fibrous carbon materials
  • fibrous carbon nanostructures such as carbon nanotubes (hereinafter sometimes referred to as “CNT”)
  • CNT consists of a cylindrical graphene sheet composed of carbon atoms, and its diameter is on the order of nanometers.
  • Fibrous carbon nanostructures such as CNTs were generally more expensive than other materials due to higher manufacturing costs. Therefore, the use thereof is limited despite having the above-mentioned excellent characteristics.
  • a CVD (Chemical Vapor Deposition) method using a catalyst (hereinafter sometimes referred to as “catalytic CVD method”) has been used as a manufacturing method capable of manufacturing CNTs and the like with relatively high efficiency. It was However, even the catalytic CVD method could not sufficiently reduce the manufacturing cost.
  • Patent Document 3 a method of producing a supported catalyst by supplying a gas containing a catalyst raw material while flowing carrier particles has been studied (see, for example, Patent Document 3). Specifically, in Patent Document 3, a supported catalyst is efficiently and uniformly obtained by spraying a catalyst component-containing liquid from above while the carrier particles are flowing.
  • the fibrous carbon nanostructure has been required to have higher quality.
  • the supported catalyst used for the production thereof be homogeneous.
  • a method for producing a supported catalyst in which a catalyst component is attached to the surface of carrier particles by spraying a suspension containing a catalytically active material as described in Patent Documents 1 and 2, and Patent Document 3
  • the catalyst raw material is applied to the surface of the carrier particles (hereinafter, also referred to as “target particles”).
  • the fluidizing gas that fluidizes the carrier particles flows from the lower side to the upper side, whereas when the suspension is sprayed from the upper side to the lower side, the sprayed suspension is pushed back upward by the flowing gas. Therefore, there is a problem that the catalytically active material does not reach the bottom of the carrier particle layer sufficiently.
  • the present invention provides a method for producing a catalyst adhering material, which can efficiently and uniformly attach a catalyst raw material to the surface of target particles, and a fibrous material using the catalyst adhering material obtained according to such a manufacturing method.
  • An object is to provide a method for producing a carbon nanostructure.
  • Another object of the present invention is to provide an apparatus for producing a catalyst adhering body, which can suitably carry out the method for producing a catalytic adhering body of the present invention.
  • an object of the present invention is to provide an apparatus for producing fibrous carbon nanostructures, which can suitably carry out the method for producing fibrous carbon nanostructures of the present invention.
  • the inventors of the present invention have made extensive studies with the aim of solving the above problems. Then, the inventors of the present invention efficiently and uniformly supply the catalyst raw material solution in the form of mist from the bottom to the top with respect to the target particles contained in the vertical container and in the fluidized state. The inventors have newly found that the raw material can be attached to the surface of the target particles, and have completed the present invention. This is because when the fluidized gas is supplied to the target particles from below to fluidize the target particles, the mist-like catalyst raw material solution is also entrained in the fluidized gas and uniformly reaches from the bottom to the top of the target particle layer. is there.
  • the method for producing a catalyst deposit of the present invention is a catalyst for attaching a catalyst raw material to the target particles using a vertical container.
  • a method for manufacturing an adhered body wherein at least one gas is supplied from a first supply port arranged in a lower portion of the vertical container toward an upper portion of the vertical container, From the flow step of flowing the target particles and the second supply port arranged in the lower part of the vertical container toward the upper direction of the vertical container, a catalyst raw material solution mist is supplied to the target particles.
  • a catalyst adhering step of adhering the catalyst raw material to obtain a catalyst adhering body and the flowing step is continued while the catalyst adhering step is carried out.
  • the method for producing a catalyst-adhered body of the present invention includes a catalyst adhering step of supplying a catalyst raw material solution mist from the lower direction to the upper direction of the vertical container for the target particles in a fluidized state, so that the method is efficient and The catalyst raw material can be uniformly attached to the surface of the target particles.
  • the first supply port and the second supply port are the same supply port, and the gas and the catalyst raw material solution mist are the same supply port through the same supply port. It is preferably introduced into a vertical container. Since the flowing gas and the catalyst raw material solution mist are introduced into the vertical container through the same supply port, the catalyst raw material can be more efficiently and uniformly attached to the surface of the target particles. .
  • the method for producing a catalyst-adhered body of the present invention includes heating the vertical container at 100 ° C. or more and 1000 ° C. or less in the catalyst adhering step.
  • the catalyst raw material can be attached to the surface of the target particles more efficiently.
  • the volume average particle diameter of the target particles is 0.1 mm or more and 1 mm or less, and the volume average particle diameter of the catalyst raw material solution mist is 1 of the volume average particle diameter of the target particles. / 10 or less, and the minimum width of the second supply port is preferably 100 times or more the volume average particle diameter of the catalyst raw material solution mist.
  • the catalyst raw material can be attached to the surface of the target particles more uniformly.
  • the second supply port for supplying the catalyst raw material solution mist when the minimum width of the second supply port for supplying the catalyst raw material solution mist is 100 times or more the volume average particle diameter of the catalyst raw material solution mist, the second supply port can be prevented from being blocked by the mist. it can.
  • the volume average particle diameter of the target particles and the volume average particle diameter of the catalyst raw material solution mist can be measured according to JIS Z8825: 2013, for example.
  • the present invention is intended to advantageously solve the above problems, the method for producing a fibrous carbon nanostructure of the present invention, the catalyst adhesion obtained according to the method for producing a catalyst adherent described above.
  • a fibrous carbon nanostructure for growing a fibrous carbon nanostructure on the catalyst adhering body obtained by passing the catalyst adhering step by supplying a carbon source gas into the vertical container. It is characterized by including a structure growing step. According to the method for producing a fibrous carbon nanostructure of the present invention, the fibrous carbon nanostructure can be efficiently produced.
  • the carbon source gas is supplied into the vertical container through a supply port different from the second supply port.
  • the fibrous carbon nanostructure grows due to the catalyst adhering material remaining near the second supply opening or the catalyst adhering near the second supply opening. It is possible to prevent the second supply port from being easily closed.
  • the catalyst attaching step and the fibrous carbon nanostructure growing step are not performed in parallel.
  • a catalyst adhering material producing apparatus of the present invention is a catalyst adhering material for adhering a catalyst raw material to target particles to obtain a catalyst adhering material.
  • a body manufacturing apparatus which has an exhaust port in an upper part and a first supply port and a second supply port in a lower part, and communicates with the vertical container through the first supply port. Through the gas supply device and the second supply port, which supply at least one gas for flowing the target particles toward the upper part of the vertical container.
  • a catalyst raw material solution mist supply device arranged so as to communicate with the catalyst raw material solution mist supply device.
  • the catalyst adhering material manufacturing apparatus for a catalyst adhering material of the present invention is a catalyst raw material for a target particle in a fluidized state by a gas supplied by at least one type of gas supply device from a lower direction to an upper direction of a vertical container. Since the catalyst raw material solution mist is supplied by the solution mist supply device, the catalyst raw material can be efficiently and uniformly attached to the surfaces of the target particles.
  • the first supply port and the second supply port are the same supply port. Since the flowing gas and the catalyst raw material solution mist are introduced into the vertical container through the same supply port, the catalyst raw material can be more efficiently and uniformly attached to the surface of the target particles. .
  • the minimum width of the second supply port is preferably 3 mm or more.
  • the minimum width of the second supply port is 3 mm or more, it is possible to prevent the second supply port from easily becoming blocked.
  • the fibrous carbon nanostructure production apparatus of the present invention includes any of the catalyst adhering body production apparatus described above, A carbon raw material gas supply device for supplying a carbon raw material gas is provided in the vertical container. According to such a manufacturing apparatus, the above-described method for manufacturing a fibrous carbon nanostructure of the present invention can be suitably implemented.
  • the carbon source gas supply device is connected to the vertical container via a supply port other than the second supply port. If the carbon raw material gas supply device is connected to the vertical container via a supply port other than the second supply port, it will adhere to the catalyst adhering material remaining near the second supply port or near the second supply port. It is possible to prevent the fibrous carbon nanostructure from growing due to the catalyst thus formed and easily blocking the second supply port.
  • the catalyst raw material which can adhere a catalyst raw material to the surface of object particle
  • a method for producing a carbon nanostructure can be provided.
  • a fibrous carbon nanostructure manufacturing apparatus capable of suitably carrying out the above-described fibrous carbon nanostructure manufacturing method of the present invention.
  • 3 is an SEM image of a catalyst adhering material after CNT synthesis according to Example 1-1.
  • 3 is an SEM image of a catalyst adhering material after CNT synthesis according to Example 1-2.
  • 5 is an SEM image of a catalyst adhering material after CNT synthesis according to Example 1-3.
  • 3 is an SEM image of a catalyst adhering material after CNT synthesis according to Example 1-4.
  • 3 is an SEM image of a catalyst adhering material after CNT synthesis according to Example 2-1.
  • 5 is an SEM image of a catalyst adhering material after CNT synthesis according to Example 2-2.
  • 5 is an SEM image of a catalyst adhering material after CNT synthesis according to Example 2-3.
  • 5 is an SEM image of a catalyst adhering material after CNT synthesis according to Example 2-4.
  • 3 is an SEM image of a catalyst adhering material after CNT synthesis according to Example 3-1.
  • 5 is an SEM image of a catalyst adhering material after CNT synthesis according to Example 3-2.
  • 5 is an SEM image of a catalyst adhering material after CNT synthesis according to Example 3-3.
  • 5 is an SEM image of a catalyst adhering material after CNT synthesis according to Example 4-1.
  • 5 is an SEM image of a catalyst adhering material after CNT synthesis according to Example 5-1.
  • 5 is an SEM image of a catalyst adhering material after CNT synthesis according to Example 5-2.
  • 5 is an SEM image of a catalyst adhering material after CNT synthesis according to Example 5-3.
  • 7 is an SEM image of a catalyst adhering material after CNT synthesis according to Example 6-1.
  • 6 is an SEM image of a catalyst adhering material after CNT synthesis according to Example 6-2.
  • 5 is an SEM image of a catalyst adhering material after CNT synthesis according to Example 6-3.
  • 5 is an SEM image of a catalyst adhering material after CNT synthesis according to Example 6-4.
  • the catalyst adhering body produced by using the method for producing a catalyst adhering body and the apparatus for producing a catalyst adhering body of the present invention is suitable for producing, for example, carbon nanotubes and fibrous carbon nanostructures such as carbon nanofibers.
  • the catalyst adhering material manufacturing apparatus of the present invention and the fibrous carbon nanostructure manufacturing apparatus including the same will be described, and then the catalyst adhering material manufacturing method and the fibrous carbon nanostructure manufacturing method of the present invention will be described.
  • the catalyst adhering material manufacturing apparatus of the present invention is a catalyst adhering material manufacturing apparatus for adhering a catalyst raw material to target particles to obtain a catalyst adhering material. Then, according to the catalyst adhered body manufacturing apparatus of the present invention, the method for manufacturing a catalyst adhered body of the present invention can be suitably implemented.
  • FIG. 1 shows a schematic structure of an example of the apparatus for producing a catalyst-adhered body of the present invention.
  • the apparatus 100 for manufacturing a catalyst deposit shown in FIG. 1 includes a vertical container 10, a gas supply device 20 for supplying at least one gas for causing target particles to flow toward the upper part of the vertical container 10, and a vertical container.
  • a catalyst raw material solution mist supply device 30 for supplying the catalyst raw material solution mist toward the upper side of the mold container 10 is provided.
  • the catalyst raw material is formed from the lower side to the upper side of the fluidized bed while flowing the target particles to form the fluidized bed. Since the solution mist can be brought into contact with the target particles, the catalyst raw material solution mist can be uniformly and efficiently supplied to the particles forming the fluidized bed. Further, in the fluidized bed, the target particles adhered by contact with the catalyst raw material solution mist can be quickly dried. Therefore, according to the catalyst adhered body manufacturing apparatus of the present invention, the catalyst raw material can be efficiently and uniformly adhered to the surfaces of the target particles.
  • the target particles to which the catalyst raw material is attached may be carrier particles to which the catalyst material has already been attached, or carrier particles to which the catalyst material has not yet been attached.
  • the carrier particles to which the catalyst material is already adhered for example, (1) before being used as a catalyst adherent, it has been used for the purpose of synthesizing fibrous carbon nanostructures, Carrier particles having a deactivated catalyst material on the surface; and (2) carrier particles that have already undergone one or more catalyst deposition operations, and that require further catalyst component deposition. Is mentioned.
  • the method for producing a catalyst adhering material of the present invention can be used for adhering the catalyst material to the carrier particles in a state where the catalyst material is not yet adhered, or the catalyst material is already adhered. It can also be used to further attach a catalyst material to the carrier particles.
  • the particles of interest can be carrier particles, specifically ceramic particles such as alumina beads, zirconia beads, quartz beads, zircon beads, and mullite beads.
  • the volume average particle diameter of the target particles can be preferably 0.1 mm or more and 1 mm or less.
  • the “particle” means an object having an aspect ratio of less than 5.
  • the aspect ratio of the target particles may be calculated by, for example, calculating a value of (maximum major axis / width orthogonal to the maximum major axis) for 100 arbitrarily selected target particles on a microscope image, and calculating an average value thereof. You can check it.
  • the volume average particle diameter of the target particles represents a particle diameter (D50) at which the cumulative volume calculated from the small diameter side is 50% in the particle size distribution (volume basis) measured according to JIS Z8825: 2013.
  • the vertical container 10 has an exhaust port 11 in the upper part and a first supply port and a second supply port in the lower part.
  • the “lower part” of the vertical container 10 refers to the lower part with reference to the position of half the length of the vertical container 10 in the height direction.
  • the vertical container 10 has the exhaust port 11 above the first supply port and the second supply port.
  • the first supply port and the second supply port may each be configured with a single opening or a plurality of openings.
  • the first supply port and the second supply port are the same supply port, and in FIG. 1, as the supply port 12 provided in the lower bottom portion of the vertical container 10.
  • the gas supply device 20 is mounted by a mist carrier gas supply unit 21 and a flowing gas supply unit 22.
  • the mist carrier gas supply unit 21 passes through the carrier gas pipe 41, the mist-containing gas pipe 42, and a part of the main pipe 43, and vertically via the supply port 12 (in this case, the “first supply port”). It is connected to the mold container 10.
  • the fluidized gas supply unit 22 is connected to the vertical container 10 via the fluidized gas pipe 44 and a part of the main pipe 43, and via the supply port 12 (in this case, the “first supply port”).
  • the catalyst raw material solution mist supply device 30 is connected to the vertical container 10 via the mist-containing gas pipe 42 and the supply port 12 (corresponding to the “second supply port” in this case).
  • the various pipes 41 to 44 may optionally include valves 51 to 54, respectively. Note that instead of or in addition to the valves 51 to 54, any member and / or device having a function of adjusting the flow rate of the fluid or object flowing in the pipe may be mounted.
  • Such members and devices are not particularly limited, and may include a pump with an inverter, a shutter, a flow meter, and the like.
  • the valve 53 arranged in the main pipe 43 may be in a closed state while the catalyst adhering step is being performed in the vertical container 10, and may be in an open state after the catalyst adhering step is completed.
  • the vertical container 10 is not particularly limited as long as it can store the target particles therein, and is a container made of a material such as stainless steel or glass.
  • the shape of the vertical container 10 is particularly limited as long as it satisfies the condition of "vertical", that is, the height of the container is larger than the maximum width in the direction perpendicular to the height direction. Without any shape.
  • the shape of the cross section perpendicular to the height direction is circular, and the cross-sectional diameter gradually decreases toward the lower end near the lower end. It is a shape having a curved portion (hereinafter, also referred to as “tapered portion”).
  • the vertical container 10 can accommodate the target particles 60 in the tapered portion and the main body portion connected to the tapered portion.
  • the taper portion can accommodate the target particles 60 and can discharge the prepared catalyst adhering body from the supply port 12 arranged at the bottom of the taper portion.
  • the target particles 60 are contained in the vertical container 10 and include at least one of carrier particles and a catalyst adhering body.
  • the vertical container 10 has a particle input port 13 at the upper part, more specifically, above the exhaust port 11, and the target particles 60 are introduced into the vertical container 10 via the particle input port 13. Can be introduced.
  • the target particles 60 form a fluidized bed inside the vertical container 10. Specifically, the target particles 60 stay and flow inside the vertical container 10 while at least a part of the target particles 60 are blown up from below through the supply port 12. Due to this flow, the catalyst raw material solution mist comes into contact with the surface of the target particles 60.
  • the gas supply device 20 exemplifies a structure including two constituent parts, a mist carrier gas supply part 21 and a flowing gas supply part 22, but in another example, the gas supply device is a flowing gas.
  • the mist carrier gas supplied from the mist carrier gas supply unit which does not include a supply unit, causes the mist to reach the vertical container, and after being introduced into the vertical container, as a gas for flowing the target particles. It is also possible to work.
  • the mist carrier gas supply unit 21 can include, for example, a tank or a cylinder that can be a supply source of the mist carrier gas, a pump, and the like.
  • the mist carrier gas is not particularly limited as long as the mist can be transported, and any gas can be used.
  • a rare gas such as argon and an inert gas such as nitrogen can be preferably used.
  • the flowing gas supply unit 22 may include, for example, a tank or a cylinder that is a supply source of the flowing gas, a pump, and the like.
  • the flowing gas the same gases as the various gases listed as the mist carrier gas can be used. Above all, from the viewpoint of cost reduction, it is preferable to use nitrogen gas as the flowing gas. Further, during the production of the catalyst-adhered body, oxygen or water vapor can be contained in the fluidized gas when the catalyst is simultaneously calcined, and hydrogen can be contained when the catalyst is simultaneously reduced.
  • the gas supply device 20 forms a fluidized bed with the target particles 60 in the vertical container 10 at a speed equal to or higher than the speed at which all the target particles 60 fall by their own weight, and the target particles 60 are outside the vertical container 10. It is preferable to allow the gas to flow into the vertical container 10 at a speed less than the speed at which the gas can be blown off. This makes it possible to keep at least a part of the target particles 60 forming the fluidized bed in the vertical container 10 in a fluidized state.
  • the falling speed can be determined based on the size and density of the target particles 60.
  • the catalyst raw material solution mist supply device 30 is not particularly limited as long as it can generate a mist from the catalyst raw material solution, and can be embodied by any mechanism, for example, using vibration, static electricity, or two fluids. And a mechanism for generating mist.
  • the catalyst raw material solution mist supply device 30 is illustrated as being a device that employs a mechanism for generating mist using vibration of ultrasonic waves.
  • the catalyst raw material solution mist generation device 30 includes a mist generation chamber 31, a vibrator 32, and a vibration control unit 33.
  • the vibration control unit 33 controls the vibrator 32 to vibrate at a predetermined frequency.
  • the oscillator 32 vibrates in the catalyst raw material solution 34, so that the catalyst raw material solution mist 35 is generated.
  • the generated catalyst raw material solution mist 35 is carried from the mist carrier gas supply unit 21 by the mist carrier gas introduced into the mist generation chamber 31 via the carrier gas pipe 41 and introduced into the mist-containing gas pipe 42. It Then, the catalyst raw material solution mist 35 carried by the mist carrier gas is introduced into the vertical container 10.
  • the vibration control unit 33 can appropriately determine conditions such as the vibration frequency of the vibrator 32 in order to generate the catalyst raw material solution mist 35 having a desired size.
  • the volume average particle diameter of the catalyst raw material solution mist is preferably 1/10 or less of the volume average particle diameter of the target particles, and more preferably 1/30 or less. By making the volume average particle diameter of the catalyst raw material solution mist to be 1/10 or less, more preferably 1/30 or less of the volume average particle diameter of the target particles, the catalyst raw material can be more uniformly applied to the surface of the target particles. Can be attached. More specifically, the volume average particle diameter of the catalyst raw material solution mist is preferably 30 ⁇ m or less, and more preferably 10 ⁇ m or less.
  • the catalyst raw material can be more uniformly attached to the surfaces of the target particles.
  • the time required for drying can be shortened, and because the mist is repelled on the surface of the target particles, so-called "stain", the adhesion of the catalyst raw material It is possible to effectively suppress the occurrence of a non-uniform portion.
  • the volume average particle diameter of the catalyst raw material solution mist can be usually 10 nm or more, or 100 nm or more.
  • volume average particle diameter of the mist represents a particle diameter (D50) at which the cumulative volume calculated from the smaller diameter side becomes 50% in the particle size distribution (volume basis) measured according to JIS Z8825: 2013. Furthermore, the volume average particle diameter of the catalyst raw material solution mist can be adjusted according to the setting of the generation device when generating the mist from the catalyst solution.
  • a solution obtained by dissolving it in a solvent such as toluene, hexane or the like can be preferably used.
  • Specific examples of such compounds include inorganic metal salts such as Al (NO 3 ) 3 , Mg (NO 3 ) 2 , Fe (NO 3 ) 3 , Co (NO 3 ) 2 and Ni (NO 3 ) 2 .
  • the present inventors have adopted a configuration in which, while fluidizing the target particles, a solution in which these compounds are dissolved is supplied as a mist, whereby the catalyst raw material is applied to the surface of the target particles. Succeeded in evenly adhering.
  • Al (NO) which is a compound containing Al as a solute is obtained.
  • the gas supply device 20 and the catalyst raw material solution mist supply device 30 are connected to the vertical container 10 via the supply port 12. Therefore, the mist containing the catalyst raw material tends to adhere to the supply port 12 and its vicinity. Then, when the target particles or the catalyst adhering material that has accidentally or somehow dropped from the fluidized bed comes into contact with the supply port 12 and its vicinity in which the mist is attached and has become wet, these target particles or The catalyst adhering material easily stays at and near the supply port 12. When such a phenomenon occurs and accumulates, the supply port 12 may finally be blocked. Therefore, in order to reduce the possibility of such blockage, it is preferable that the minimum width of the supply port 12 is 3 mm or more.
  • the minimum width of the supply port 12 is preferably 100 times or more, and more preferably 300 times or more of the volume average particle diameter of the catalyst raw material solution mist.
  • the volume average particle diameter of the catalyst raw material solution mist is preferably 1/100 or less of the minimum width of the supply port 12, and more preferably 1/300 or less.
  • “the minimum width of the supply port” specifically means (1) the diameter of the circle when the opening shape of the supply port is a circle; (2) the opening shape of the supply port is an ellipse. (3) When the opening shape of the supply port is rectangular, it means the length of the short side; (4) When the opening shape of the supply port is slit-shaped, it means the slit shape. Means minimum width.
  • the opening shape of the supply port 12 is preferable.
  • the features described above are shown as the features.
  • the gas supply unit and the catalyst raw material solution mist supply device are connected to the vertical container 10 via different supply ports, that is, the gas is supplied via the first supply port.
  • the opening shapes of the two supply ports satisfy various conditions as described above.
  • the catalyst adhered body manufacturing apparatus 100 further includes a heating device 70 configured to be able to heat the inside of the vertical container 10.
  • the heating device 70 is not particularly limited and may be configured by various heaters, for example. Further, the heating device 70 can heat the vertical container 10 to preferably 100 ° C. or higher, more preferably 200 ° C. or higher, preferably 1000 ° C. or lower, more preferably 900 ° C. or lower.
  • the heating temperature can be optimized according to the type and properties of the catalyst raw material solution to be used, the flow rate at the time of supplying the flowing gas and the mist carrier gas, and the like. Further, the temperature inside the heated vertical container 10 can also be within the above-mentioned preferable range.
  • the catalyst adhering material manufacturing apparatus 100 includes a recovery device 80 configured to recover the catalyst adhering material prepared in the vertical container 10.
  • the recovery device 80 is preferably located below the vertical container 10. According to this configuration, the catalyst adhering material can be efficiently recovered by recovering the catalyst adhering material below the vertical container via the supply port 12.
  • a recovery chamber constituting a recovery device 80 is connected via a main pipe 43 connected to the supply port 12 located at the lower end of the vertical container 10.
  • the mist-containing gas pipe connection port 46 which is the connection port for connecting the mist-containing gas pipe 42 to the main pipe 43, and the flowing gas pipe 44 to the main pipe 43. It is preferable that it is arranged on the upper side (that is, on the side closer to the vertical container 10) than the fluidized gas pipe connection port 47 which is a connection port connected to it. Since the catalyst raw material solution mist passes through the upper portion of the main pipe 43, more specifically, the inner wall above the connection position of the mist-containing gas pipe connection port 46, the catalyst adhering step is performed during the catalyst adhering step. Easy to get wet.
  • the fluid gas pipe connection port 47 is located below the mist-containing gas pipe connection port 46, the fluid gas passing through the fluid gas pipe connection port 47 and the main pipe 43 causes the inner wall of the upper portion of the main pipe 43 to move, It is possible to dry prior to recovery.
  • the relative positional relationship between the mist-containing gas pipe connection port 46 and the flowing gas pipe connection port 47 as described above, it is possible to prevent the catalyst deposit from being trapped on the wet inner wall, and Collection can be facilitated.
  • the catalyst raw material can be efficiently and uniformly attached to the surfaces of the target particles.
  • the lower portion of the vertical container provided in the apparatus for producing a catalyst-adhered body be provided with the tapered portion as shown in FIG. That is, in a modification, the bottom of the vertical container is a plane orthogonal to the height direction, and a small space is left from the bottom so as to function as a dispersion plate that disperses the gas and the catalyst raw material solution mist. May be provided. Inside the vertical container having such a structure, at least a part of the target particles is supported by the porous plate.
  • the second supply port on the upper surface or above the perforated plate by using a pipe penetrating the perforated plate.
  • the configuration in which the recovery chamber configuring the recovery device 80 is connected via the main pipe 43 connected to the supply port 12 located at the lower end of the vertical container 10 is illustrated.
  • the connection mode of is not limited to this configuration.
  • the recovery chamber may be arranged so as to communicate with the vertical container through a recovery port provided at any one of the upper portion, the lower portion, and the side portion of the vertical container. In this case, by supplying a large amount of flowing gas to the vertical container, the catalyst adhering material can be carried to the recovery port.
  • the catalyst adhered body may be collected above the vertical container.
  • the catalyst adhered body manufacturing apparatus may be provided with a mechanism capable of inclining or rotating the vertical container, if necessary. According to the catalyst deposit manufacturing apparatus having such a configuration, the catalyst deposits are collected by opening the recovery ports provided at various positions and tilting or rotating the vertical container as necessary. You can
  • the first supply port (the supply port for the gas that causes the target particles to flow) and the second supply port (the supply port for the catalyst raw material solution mist) arranged at the bottom of the vertical container are the same supply port 12
  • the first supply port 14 and the second supply port 15 are mounted as different supply ports, as in a catalyst adhered body manufacturing apparatus 100 ′ whose schematic configuration is illustrated in FIG. May be.
  • each component corresponding to each component shown in FIG. 1 is denoted by the same reference numeral, and although the configuration and function shown in FIG. The different components are indicated by the same reference numerals with "'" added.
  • the fluidized gas supply unit 22 ′ communicates with the vertical container 10 ′ via the fluidized gas pipe 44 ′ having the valve 54 ′ and the first supply port 14.
  • the catalyst raw material solution mist supply device 30 is arranged so as to communicate with the vertical container 10 ′ via the second supply port 15. Therefore, the fluidized gas supplied from the fluidized gas supply unit 22 ′ and transferred through the fluidized gas pipe 44 ′ is supplied into the vertical container 10 ′ via the first supply port 14.
  • the first supply port 14 shown in FIG. 2 is mounted as a plurality of holes (or slits) provided in a tapered porous plate whose bottom is connected to the second supply port 15. The fluidized gas that has passed through the first supply port 14 functions to fluidize the target particles.
  • the first supply port 14 is illustrated as a plurality of holes provided in the porous plate, but the number of the first supply ports 14 may be one.
  • the shape of the tapered porous plate whose bottom is connected to the second supply port 15 is not limited to the tapered shape, and may be any shape.
  • FIG. 3 shows a schematic configuration of a fibrous carbon nanostructure manufacturing apparatus 200 of the present invention including the catalytic deposit manufacturing apparatus 100 of the present invention described above with reference to FIG.
  • the fibrous carbon nanostructure manufacturing apparatus 200 is an apparatus in which a carbon source gas supply device 90 is connected to the catalyst-adhered material manufacturing apparatus described with reference to FIG.
  • the carbon raw material gas supply device 90 is connected to the vertical container 10 via the carbon raw material supply pipe 45, a part of the flowing gas pipe 44, and a part of the main pipe 43.
  • the fibrous carbon nanostructure manufacturing apparatus 200 may include a control device (not shown).
  • the carbon raw material gas supply device 90 is not particularly shown in detail, but is not particularly limited as long as it can supply a gas containing a carbon raw material that can be a material for producing a fibrous carbon nanostructure, and a tank and It includes a carbon source gas supply source that can be mounted by a cylinder or the like, a pump, and the like.
  • Known carbon raw materials can be used, for example, carbon alkynes and alkenes (olefin hydrocarbons), alkanes (paraffin hydrocarbons), alcohols, ethers, aldehydes, ketones, aromatic hydrocarbons, and carbon monoxide.
  • the carbon raw material gas may contain a rare gas such as argon, an inert gas such as nitrogen, a reducing gas such as hydrogen, and / or an oxygen element-containing gas such as carbon dioxide.
  • the fibrous carbon nanostructure manufacturing apparatus 200 drives the carbon source gas supply device 90 in a state in which the activated catalyst adhering material is accommodated, so that the fibrous carbon adhering material is formed on the catalyst adhering material in the vertical container 10.
  • Carbon nanostructures can be synthesized.
  • the activated catalyst adhering material is, for example, brought into contact with a reducing gas such as hydrogen, ammonia, methane or the like while the catalyst adhering material prepared in the vertical container 10 is accommodated in the vertical container 10. Can be obtained.
  • the control device (not shown), which has an arbitrary configuration, includes a catalyst raw material solution mist supply device 30 for supplying the catalyst raw material solution mist into the vertical container 10 and a carbon raw material gas supply device 90 for inside the vertical container 10. It is possible to control the supply of the carbon raw material gas to the catalysts in parallel, that is, the supply of the catalyst raw material solution mist and the supply of the carbon raw material gas in terms of time.
  • the catalyst raw material solution mist and the carbon raw material gas are not simultaneously supplied into the vertical container 10, in other words, the catalyst raw material solution mist is supplied into the vertical container 10 during the synthesis of the fibrous carbon nanostructure. If it does not exist, it is possible to prevent the fibrous carbon nanostructures from being adsorbed and mixed with the catalyst raw material to reduce the purity of the fibrous carbon nanostructures.
  • the supply port 12 provided at the bottom (lower part) of the vertical container 10 can also function as a recovery port, that is, a gas for flowing target particles is introduced into the vertical container 10.
  • the first supply port for supplying the catalyst raw material solution mist and the second supply port for introducing the catalyst raw material solution mist into the vertical container 10 also serve as the recovery port.
  • the configuration of the recovery port is not limited to such an aspect, and in a modified example, the vertical container 10 may have a recovery port on the side portion or the upper part.
  • the carbon source gas supply device 90 is illustrated as being connected to the vertical container 10 via the carbon source supply pipe 45, a part of the flowing gas pipe 44, and a part of the main pipe 43. did.
  • the connection mode of the carbon source gas supply device 90 to the vertical container 10 is not limited to the illustrated mode.
  • the carbon source gas supply device 90 is preferably connected to the vertical container 10 in such a manner that the carbon source gas is circulated from the lower side to the upper side in the vertical container 10.
  • FIG. 4 shows a schematic configuration of a fibrous carbon nanostructure manufacturing apparatus 200 ′ according to another embodiment of the present invention, which includes the catalyst adhered material manufacturing apparatus 100 ′ shown in FIG. 2.
  • each component corresponding to each component shown in FIGS. 1 to 3 is denoted by the same reference numeral.
  • the carbon raw material gas supply device and the carbon raw material supply pipe which are different in arrangement from the fibrous carbon nanostructure manufacturing apparatus 200 according to FIG. 3, the same reference numerals are denoted by “′”.
  • the carbon raw material gas supply device 90 ′ includes a carbon raw material supply pipe 45 ′, a part of the flowing gas pipe 44 ′ having a valve 54 ′, and the first supply port 14. And is connected to the vertical container 10 '. Then, the carbon source gas supplied from the carbon gas supply device 90 ′ is mixed with the flowing gas at the confluence with the flowing gas pipe 44 ′, and then the vertical container 10 ′ via the first supply port 14. Will be introduced in. According to this structure, the carbon source gas is introduced into the vertical container 10 ′ via the first supply port 14, which is a supply port different from the second supply port 15 to which the catalyst raw material solution mist is supplied.
  • the carbon gas supply device is arranged so as to communicate with the vertical container via a supply port different from both the first supply port and the second supply port. It may be.
  • the method for producing a catalyst-adhered body comprises a flow step of supplying at least one kind of gas in an upward direction from a first supply port arranged at a lower portion of a vertical container to flow target particles, and a vertical container.
  • a catalyst adhering step of supplying a catalyst raw material solution mist from the second supply port arranged in the lower part of the catalyst toward the upper side to adhere the catalyst raw material to the target particles to obtain a catalyst adhering body, The flow process is continued while the process is performed.
  • the method for producing a catalyst-adhered body of the present invention includes a catalyst adhering step of supplying a catalyst raw material solution mist from the lower direction to the upper direction of the vertical container for the target particles in a fluidized state, so that the method is efficient and The catalyst raw material can be uniformly attached to the surface of the target particles.
  • a catalyst adhering step of supplying a catalyst raw material solution mist from the lower direction to the upper direction of the vertical container for the target particles in a fluidized state, so that the method is efficient and The catalyst raw material can be uniformly attached to the surface of the target particles.
  • each step will be described in detail.
  • the method for producing a catalyst deposit according to the present invention can be suitably carried out by the above-described apparatus for producing a catalyst deposit according to the present invention.
  • a case where the method for producing a catalyst-adhered body of the present invention is carried out using the apparatus for producing a catalyst-adhered body of the present invention will be described.
  • the target particles 60 are contained in the vertical container 10.
  • the target particles 60 particles such as those described in detail in the item (Catalyst Adhesion Body Manufacturing Apparatus) can be preferably used.
  • a specific method for accommodating the target particles 60 in the vertical container 10 in the preparation step for example, as shown in FIG. 1, from the particle inlet 13 provided in the upper portion of the vertical container 10, Including the target particles 60 in the vertical container 10.
  • the gas supply device 20 is driven to supply at least one kind of gas toward the upper part of the vertical container 10 from the supply port 12 arranged in the lower part to cause the target particles 60 to flow.
  • the “at least one gas” includes the mist carrier gas derived from the mist carrier gas supply unit 21 and the fluid gas derived from the fluid gas supply unit 22.
  • the mist carrier gas is the mist. It functions not only as a carrier but also as a gas for causing the target particles 60 to flow.
  • mist carrier gas is a mist carrier that conveys mist while the catalyst raw material solution mist supply device 30 is not driven. Instead, it may function purely as a gas for causing the target particles 60 to flow.
  • the gas described in detail in the section can be preferably used. Further, it is preferable that the inflow rates of these gases be the rates described in detail in the section of (Catalyst adherent manufacturing apparatus).
  • the catalyst raw material solution mist is supplied from the supply port 12 arranged at the lower portion of the vertical container 10 toward the upper portion of the vertical container 10 so that the catalyst raw material is supplied to the target particles 60 in a fluid state. Are attached to obtain a catalyst-adhered body. More specifically, in the catalyst adhering step, the catalyst raw material solution mist supply device 30 is driven to generate a catalyst raw material solution mist, which is entrained in the mist carrier gas supplied from the mist carrier gas supply unit 21, It is introduced into the vertical container 10 from below. Since the catalyst raw material solution mist flows together with the flowing gas from the lower side to the upper side in the vertical container 10, the catalyst raw material can be uniformly and uniformly attached to the surface of the target particles.
  • the volume average particle diameter of the catalyst raw material solution mist generated by the catalyst raw material solution mist supply device 30 is the same as that described in the preferred embodiment in the section of (Catalyst adhering body manufacturing device) It is preferably 1/10 or less of the particle diameter, more preferably 1/30 or less, and preferably 1/100 or less of the minimum width of the supply port 12, and 1/300 or less. Is more preferable.
  • the specific value of the volume average particle size of the catalyst raw material solution mist is also preferably 30 ⁇ m or less, more preferably 10 ⁇ m or less, and usually 10 nm or more, or 100 nm or more. .
  • the target particles 60 may be in a fluid state.
  • the heating device 70 is activated to heat the vertical container 10 at preferably 100 ° C. or higher, more preferably 200 ° C. or higher, preferably 1000 ° C. or lower, more preferably 900 ° C. or lower. Is more preferable.
  • the heating of the vertical container 10 may be continued at the timing before and after the catalyst adhering step.
  • the heating temperature can be optimized according to the type and properties of the catalyst raw material solution to be used, the flow rate at the time of supplying the flowing gas and the mist carrier gas, and the like.
  • the mist generated from the catalyst raw material solutions having different compositions may be switched for a predetermined time and supplied to the vertical container 10.
  • a plurality of layers having different compositions can be formed on the surface of the target particles according to the composition of the catalyst raw material solution mist.
  • the flow rate of the gas introduced into the vertical container 10 is reduced or set to zero so that the particles (catalyst adhering body) having the catalyst adhered thereto are flowed down and collected.
  • the gas supply device 20 is kept driven for a short period of time to continue the flowing step, and the mist adheres to a wet state. It is preferable to dry the upper part of the main pipe 43 and the vicinity of the supply port 12 where
  • a fibrous carbon nanostructure is produced using the catalyst adhering material obtained according to the above-mentioned method for producing a catalytic adhering material of the present invention. Then, the method for producing a fibrous carbon nanostructure of the present invention is to supply a carbon raw material gas into a vertical container to form a fibrous carbon nanostructure on the catalyst adhering body obtained through the catalyst adhering step. The step of growing fibrous carbon nanostructures is included.
  • a carbon source gas is supplied to the activated catalyst deposit to grow the fibrous carbon nanostructure on the catalyst deposit. It is preferable not to carry out the fibrous carbon nanostructure growing step in parallel with the catalyst attaching step. By carrying out the catalyst attachment step and the fibrous carbon nanostructure growing step separately in time, it is possible to prevent the catalyst raw material from adhering and mixing into the obtained fibrous carbon nanostructure. it can.
  • the method for obtaining the activated catalyst deposit used in this step and the carbon raw material that can be contained in the carbon raw material gas are as described in detail in the section of (Fibrous carbon nanostructure production apparatus). is there.
  • the supply port for introducing the catalyst raw material solution mist into the vertical container it is different from the supply port for supplying the catalyst raw material solution mist into the vertical container. It is preferable to supply the carbon raw material into the vertical container through the supply port.
  • the fibrous carbon nanostructure growth step can be performed in the vertical container 10.
  • the method for producing the fibrous carbon nanostructure according to the present invention is not limited to this, and it is of course possible to carry out the fibrous carbon nanostructure growth step in a separate reaction vessel. In such a case, for example, by accommodating the catalyst adhering material in an air flow bed synthesizer, a fixed bed synthesizer, a moving bed synthesizer, a fluidized bed synthesizer, or the like according to a known apparatus configuration, activation, carbon material gas Through the supply, the fibrous carbon nanostructure can be synthesized.
  • the catalyst-adhered material having the fibrous carbon nanostructures obtained on the surface in the fibrous carbon nanostructure growth step has a large amount of, for example, a rare gas such as argon or an inert gas such as nitrogen. It can be supplied at a flow rate and transferred to a separator, where it can be separated and recovered from an inert gas stream by gravity settling, centrifugation, filtration or the like. Alternatively, from the first supply port, the second supply port, and / or the recovery port installed below the vertical container 10, the catalyst adhering body having the obtained fibrous carbon nanostructure on the surface is gravity-fed. The sediment may be collected downward from the vertical container 10.
  • a rare gas such as argon
  • an inert gas such as nitrogen
  • the catalyst adhering material having the recovered fibrous carbon nanostructures is not particularly limited, and for example, the fibrous carbon nanostructures can be prepared by a relatively simple method such as shaking or being put into a liquid and stirred. It can be separated into a body and a catalyst-attached body.
  • the CNT yield was calculated as the ratio of the mass difference (mg CNTs ) of the catalyst adhering material before and after the CNT synthesis to the mass of the catalyst adhering material before CNT synthesis (g Beads ).
  • Example 1-1 ⁇ Production of catalyst adhering material> A catalyst adhering material manufacturing apparatus having a schematic structure as shown in FIG. 1 was used to manufacture a catalyst adhering material according to the following steps, and the obtained catalyst adhering material was used to synthesize CNT in a fixed bed.
  • ⁇ Preparation process >> Al (NO 3 ) 3 that is a compound containing Al and Fe (NO 3 ) 3 that is a compound containing Fe are dissolved in ion-exchanged water to obtain a mixed aqueous solution as a catalyst raw material solution.
  • the amount of each compound used was such that the Fe concentration was 30 mM and the Al concentration was 30 mM in the mixed aqueous solution. Further, 30 g of zirconia (ZrO 2 ) beads having a volume average particle diameter of 0.3 mm as target particles were accommodated in the vertical container from a particle inlet provided on the upper part of the vertical container. The preset temperature (heating temperature) of the heating device was set to 150 ° C., and heating of the vertical container was started. ⁇ Flow process >> The fluidized gas supply unit is driven to supply nitrogen gas as a fluidized gas from the lower part of the vertical container to the upper direction at a flow rate of 4.5 slm from the supply port to start the flow of the zirconia beads.
  • a fluidized bed was formed. Further, the gas flow rate of the argon gas was set to 0.5 slm, and the operation of the mist carrier gas supply unit was started.
  • the argon gas functions as a gas for causing the target particles to flow when the catalyst raw material solution mist supply device is not driven.
  • Catalyst attachment step >> The catalyst raw material solution mist supply device was set so that the volume average particle diameter D50 of the generated mist was in the range of 1 ⁇ m or more and 5 ⁇ m or less, and the operation was started.
  • the catalyst raw material solution mist was carried by the mist carrier gas supplied from the mist carrier gas supply unit, and the catalyst raw material solution mist was supplied from the lower part of the vertical container to the upper direction through the supply port.
  • the supply of the catalyst raw material solution mist, the mist carrier gas, and the flowing gas was continued for 10 minutes and then stopped, and the catalyst adhesion step was completed.
  • ⁇ Recovery process After the timing of completing the catalyst adhering process, the valve provided in the main pipe (corresponding to the main pipe 43 in FIG. 1) connected to the supply port is opened, and the recovery device (corresponding to the recovery device 80 in FIG. 1). The catalyst adhering material was allowed to flow down and was collected.
  • ⁇ Fibrous carbon nanostructure growth process >> The catalyst deposit collected in the collecting step was filled in a fixed bed apparatus for synthesizing carbon nanotubes equipped with a horizontal furnace, and the temperature inside the fixed bed apparatus for CNT synthesis was raised to 800 ° C.
  • Examples 1-2 to 1-4 Fe concentration and Al concentration in mixed aqueous solution as catalyst raw material solution, set temperature of heating device, nitrogen gas (fluid gas) flow rate, argon gas (mist carrier gas) flow rate, and / or continuation of ⁇ Catalyst adhesion step >>
  • a catalyst deposit was produced in the same manner as in Example 1-1, except that the times (supporting times) were changed as shown in Table 1, and CNT was synthesized using the obtained catalyst deposit. Further, various evaluations and measurements were performed according to the above. The results are shown in Table 1.
  • Example 2-1 Using the apparatus having the same structure as the apparatus for producing a catalyst deposit used in Examples 1-1 to 1-4, a catalyst deposit was produced according to the following steps, and the obtained catalyst deposit was used to form a fixed bed. To synthesize CNT.
  • ⁇ Preparation process A mixed ethanol solution was prepared in which Al (Oi-Pr) 3 which is a compound containing Al and Fe (C 5 H 5 ) 2 which is a compound containing Fe were used in combination. The amount of each compound used was such that the Fe concentration in the mixed ethanol solution was 22.5 mM and the Al concentration was 27.5 mM.
  • zirconia (ZrO 2 ) beads having a volume average particle diameter of 0.3 mm as target particles were accommodated in the vertical container from a particle inlet provided on the upper part of the vertical container.
  • the preset temperature of the heating device was set to 550 ° C., and heating of the vertical container was started.
  • ⁇ Flow process By driving the fluidized gas supply unit, nitrogen gas as a fluidized gas is supplied from the supply port from the lower part of the vertical container to the upper direction at a flow rate of 1 slm to start the fluidization of zirconia beads to form a fluidized bed. Was formed. Further, the gas flow rate of the argon gas was set to 4 slm, and the operation of the mist carrier gas supply unit was started.
  • Catalyst attachment step The catalyst raw material solution mist supply device was set so that the volume average particle diameter D50 of the generated mist was in the range of 1 ⁇ m or more and 5 ⁇ m or less, and the operation was started.
  • the catalyst raw material solution mist was carried by the mist carrier gas supplied from the mist carrier gas supply unit, and the catalyst raw material solution mist was supplied from the lower part of the vertical container to the upper direction through the supply port.
  • the supply of the catalyst raw material solution mist, the mist carrier gas, and the flowing gas was continued for 30 minutes and then stopped, and the catalyst adhesion step was completed.
  • Example 2-2 to 2-4 A catalyst deposit was produced in the same manner as in Example 2-1 except that the set temperatures of the heating devices were changed as shown in Table 1, and CNT was synthesized using the obtained catalyst deposit. Further, various evaluations and measurements were performed according to the above. The results are shown in Table 1.
  • Examples 3-1 to 3-3 Fe concentration and Al concentration in mixed aqueous solution as catalyst raw material solution, set temperature of heating device, nitrogen gas (fluid gas) flow rate, argon gas (mist carrier gas) flow rate, and / or continuation of ⁇ Catalyst adhesion step >>
  • a catalyst-adhered material was produced in the same manner as in Example 1-1, except that the time (supporting time) was changed as shown in Table 1. The obtained catalyst-adhered material was used to synthesize CNT in a fluidized bed.
  • Example 4-1 Other than changing the compounding amounts of the respective compounds so that the Fe concentration and the Al concentration in the mixed ethanol solution are as shown in Table 1, and further changing the set temperature of the heating device as shown in Table 1, In the same manner as in Example 2-1, a catalyst-adhered body was produced and CNT was synthesized. Further, various evaluations and measurements were performed according to the above. The results are shown in Table 1.
  • Examples 5-1 to 5-3 Using the apparatus having the same structure as the apparatus for producing a catalyst adhering material used in Example 1-1 and the like, a catalyst adhering material was manufactured according to the following steps, and the obtained catalyst adhering material was used to produce CNT in a fluidized bed. Synthesized. More specifically, in ⁇ Catalyst Adhesion Step >>, two kinds of solutions having different compositions as shown in Table 2 are used as the catalyst raw material solution, and these solutions are formed at predetermined time intervals shown in Table 2. The mist was switched and supplied to a vertical container to obtain a catalyst adhering material. The obtained catalyst-adhered body had a layer containing Fe and Al and a layer containing Fe formed in this order on the surface of the target particle.
  • each layer was a thickness according to the supply time of the mist of each solution. Then, using the catalyst-adhered material, CNTs were synthesized under the same conditions as in Examples 3-1 to 3-3. Further, various evaluations and measurements were performed according to the above. The results are shown in Table 2.
  • Example 6-1 to 6-3 In ⁇ Catalyst Adhesion Step >>, as the catalyst raw material solution, two kinds of solutions as shown in Table 2 were used except that Fe concentration and Al concentration were as shown in Table 2, respectively. A catalyst-adhered material was obtained according to the same conditions as in Example 5-2. Then, using the obtained catalyst-adhered material, CNT was synthesized under the same conditions as in Examples 3-1 to 3-3. Further, various evaluations and measurements were performed according to the above. The results are shown in Table 2.
  • the method for producing a catalyst adhering material of the present invention which includes a catalyst adhering step of supplying a catalyst raw material solution mist from the lower direction to the upper direction of a vertical container for target particles in a fluidized state.
  • a catalyst adhering step of supplying a catalyst raw material solution mist from the lower direction to the upper direction of a vertical container for target particles in a fluidized state.
  • the timing at which the mist reaches the surface of the target particles and the drying speed of the mist can be well balanced.
  • the nitrogen gas and argon gas flow rate conditions are Then, it is understood that it is preferable to set the set temperature of the heating device to 600 ° C. or higher and 850 ° C. or lower.
  • the catalyst component is well adhered to the surface of the target particle. It is thought that this is because it can be done. Furthermore, for example, from Examples 3-1 to 3-3 and Example 4-1, the catalyst component can be favorably adhered to the surface of the target particle under various conditions, and the obtained catalyst adhering material It can be seen that CNT could be satisfactorily synthesized by using.
  • the catalyst raw material which can adhere a catalyst raw material to the surface of object particle
  • a method for producing a carbon nanostructure can be provided.
  • a fibrous carbon nanostructure manufacturing apparatus capable of suitably carrying out the above-described fibrous carbon nanostructure manufacturing method of the present invention.

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Abstract

L'invention concerne un procédé de production d'un corps adhéré à un catalyseur, comprenant une étape d'écoulement consistant à fournir du gaz vers le haut à partir d'un orifice d'alimentation agencé au niveau de la partie inférieure d'un récipient vertical 10 afin d'amener des particules cibles 60 à s'écouler, et une étape d'adhérence de catalyseur consistant à fournir une brume de solution de matière première de catalyseur vers le haut à partir de l'orifice d'alimentation afin de faire adhérer la matière première de catalyseur aux particules cibles 60 et obtenir un corps adhérant à un catalyseur, les deux étapes étant mises en oeuvre simultanément.
PCT/JP2019/040739 2018-10-25 2019-10-16 Procédé et appareil de production d'un corps adhéré à un catalyseur, et procédé et appareil de production de nanostructure de carbone fibreux WO2020085170A1 (fr)

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JP2005502446A (ja) * 2001-03-30 2005-01-27 カウンシル オブ サイエンティフィック アンド インダストリアル リサーチ 新規の触媒処方物およびその調製
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JP2010527777A (ja) * 2007-05-31 2010-08-19 ズード−ケミー アーゲー シェル触媒の製造方法およびそのシェル触媒
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JP2005502446A (ja) * 2001-03-30 2005-01-27 カウンシル オブ サイエンティフィック アンド インダストリアル リサーチ 新規の触媒処方物およびその調製
JP2007506540A (ja) * 2003-09-26 2007-03-22 ビーエーエスエフ　アクチェンゲゼルシャフト 流動床中で粉末状、粒状または成形したばら材料を混合し、乾燥し、被覆する装置および前記装置を使用して担持触媒を製造する方法
JP2010527777A (ja) * 2007-05-31 2010-08-19 ズード−ケミー アーゲー シェル触媒の製造方法およびそのシェル触媒
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