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WO2018160041A1 - Procédé de fabrication de nanotubes de carbone à parois multiples à l'aide d'un processus de type continu - Google Patents

Procédé de fabrication de nanotubes de carbone à parois multiples à l'aide d'un processus de type continu Download PDF

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Publication number
WO2018160041A1
WO2018160041A1 PCT/KR2018/002548 KR2018002548W WO2018160041A1 WO 2018160041 A1 WO2018160041 A1 WO 2018160041A1 KR 2018002548 W KR2018002548 W KR 2018002548W WO 2018160041 A1 WO2018160041 A1 WO 2018160041A1
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Prior art keywords
carbon nanotubes
walled carbon
catalyst powder
reactor
producing
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English (en)
Korean (ko)
Inventor
류상효
성현경
정충헌
김동환
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Kumho Petrochemical Co Ltd
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Korea Kumho Petrochemical Co Ltd
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Priority claimed from KR1020180024472A external-priority patent/KR102053726B1/ko
Application filed by Korea Kumho Petrochemical Co Ltd filed Critical Korea Kumho Petrochemical Co Ltd
Priority to JP2019548043A priority Critical patent/JP6872627B2/ja
Priority to CN201880023603.XA priority patent/CN110494390A/zh
Priority to US16/490,772 priority patent/US11117803B2/en
Publication of WO2018160041A1 publication Critical patent/WO2018160041A1/fr
Anticipated expiration legal-status Critical
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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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • 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
    • 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
    • C01B32/164—Preparation involving continuous processes
    • 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/30—Scanning electron microscopy; Transmission electron microscopy

Definitions

  • the present invention relates to a method for producing multi-walled carbon nanotubes using a continuous process.
  • Carbon nanotube is a hexagonal honeycomb tubular structure in which one carbon atom is bonded to three other carbon atoms, and its electrical, thermal, and mechanical properties are superior to other materials to be applied to various industrial fields. have.
  • Such carbon nanotubes are generally arc-discharge, pyrolysis, laser vaporization, chemical vapor deposition, plasma chemical vapor deposition, thermal It is prepared by various methods such as thermal chemical vapor deposition, chemical vapor condensation, and the like.
  • the production method of the catalyst is spray drying (spray dry) is made at a low temperature of 200 ⁇ 350 °C, in order to form a hole in the catalyst, it is essential to use a water-soluble polymer as a pore-forming agent, making the catalyst in a form suitable for synthesis
  • spray drying spray dry
  • a water-soluble polymer as a pore-forming agent
  • the present invention is to solve the above-mentioned problems of the prior art, an object of the present invention is to improve the conversion of the carbon-based raw material gas and the yield of the multi-walled carbon nanotubes by using the catalyst powder optimized for the fluidized bed reactor It is to provide a method for producing a large amount of nanotubes.
  • One aspect of the invention (a) dissolving the metal precursor in a solvent to prepare a precursor solution; (b) pyrolysing the precursor solution while spraying into the reactor to form a catalyst powder; And (c) synthesizing the multi-walled carbon nanotubes from the catalyst powder by injecting the catalyst powder into a fluidized bed reactor heated to 600 to 900 ° C. and injecting a carbon gas and a carrier gas. Step a) to (c) is carried out continuously, the catalyst powder provides a method for producing a multi-walled carbon nanotubes comprising a metal component according to the following formula (1).
  • Ma is at least two metals selected from Fe, Ni, Co, Mn, Cr, Mo, V, W, Sn and Cu
  • Mb is at least one metal selected from Mg, Al, Si and Zr
  • the catalyst powder may have a hollow structure having a thickness of 0.5 ⁇ 10 ⁇ m.
  • the apparent density of the catalyst powder may be 0.05 ⁇ 0.70 g / mL.
  • the hollow ratio of the hollow structure may be more than 50% by volume.
  • the conversion rate according to Equation 2 may be 80% or more.
  • Conversion rate (%) ⁇ (weight of multi-walled carbon nanotubes (g))-(weight of catalyst powder (g)) ⁇ / ⁇ (carbon-based gas supply (L)) * (of carbon in 1 mol of carbon-based gas) Weight (g / mol)) / (22.4 (L / mol)) ⁇ * 100
  • the carbon-based gas may be one selected from the group consisting of saturated or unsaturated hydrocarbons having 1 to 4 carbon atoms, carbon monoxide, benzene, and mixtures of two or more thereof.
  • the carrier gas may be one selected from the group consisting of helium, nitrogen, argon, and mixtures of two or more thereof.
  • the metal precursor may be one selected from the group consisting of nitrates, sulfates, alkoxides, chlorides, acetates, carbonates, and mixtures of two or more thereof.
  • the step (b) comprises the steps of (i) spraying the precursor solution into the reactor by supplying air of 2 to 5 atm as a carrier gas and introducing external air; And (ii) pyrolyzing the sprayed precursor solution at 600 to 1,200 ° C. to form a catalyst powder.
  • the step (c) comprises: (i) heating the fluidized bed reactor to 600 ⁇ 900 °C; (ii) feeding catalyst powder at the top of the reactor and fluidizing in the reactor; (iii) supplying a carbonaceous gas and a carrier gas through a rotary blade at the bottom of the reactor; And (iv) thermally vapor-depositing carbon on the catalyst powder fluidized by an upward air flow by the rotary blades.
  • step (d) recovering the multi-walled carbon nanotubes from the fluidized bed reactor may be further included.
  • the step (d) comprises the steps of: (i) transferring the multi-walled carbon nanotubes to a cyclone using nitrogen gas; And (ii) screening the multi-walled carbon nanotubes by removing impurities from the multi-walled carbon nanotubes in the cyclone.
  • the multi-walled carbon nanotubes may be aggregated to exist as a bundle-type carbon nanotubes.
  • the average bundle diameter of the bundle-type carbon nanotubes may be 0.5 ⁇ 20 ⁇ m
  • the average bundle length (bundle length) may be 10 ⁇ 200 ⁇ m.
  • the Raman spectral intensity ratio (I G / I D ) of the multi-walled carbon nanotubes may be 0.7 ⁇ 1.5.
  • the average diameter of the multi-walled carbon nanotubes may be 5 ⁇ 50nm.
  • the apparent density of the multi-walled carbon nanotubes may be 0.01 ⁇ 0.07g / mL.
  • FIG. 1 is an SEM image of a catalyst for preparing multi-walled carbon nanotubes according to an embodiment of the present invention.
  • FIG. 2 is an SEM image of a catalyst for preparing multi-walled carbon nanotubes according to a comparative example of the present invention.
  • One aspect of the invention (a) dissolving the metal precursor in a solvent to prepare a precursor solution; (b) pyrolysing the precursor solution while spraying into the reactor to form a catalyst powder; And (c) synthesizing the multi-walled carbon nanotubes from the catalyst powder by injecting the catalyst powder into a fluidized bed reactor heated to 600 to 900 ° C. and injecting a carbon gas and a carrier gas. Step a) to (c) is carried out continuously, the catalyst powder provides a method for producing a multi-walled carbon nanotubes comprising a metal component according to the following formula (1).
  • Ma is at least two metals selected from Fe, Ni, Co, Mn, Cr, Mo, V, W, Sn and Cu
  • Mb is at least one metal selected from Mg, Al, Si and Zr
  • the step (a) it can be prepared a precursor solution of each metal element constituting the catalyst powder.
  • the metal precursor may be one selected from the group consisting of nitrates, sulfates, alkoxides, chlorides, acetates, carbonates, and mixtures of two or more thereof, but is not limited thereto.
  • the solvent may be a polar solvent, and water, methanol, ethanol, propanol, isopropanol, butanol, or a mixed solvent of two or more thereof may be used as the polar solvent, preferably, water, more Preferably, deionized water can be used.
  • the precursor solution may be pyrolyzed while being sprayed into the reactor to form a catalyst powder.
  • Step (b) may include: (i) spraying a precursor solution into the reactor by supplying air of 2 to 5 atmospheres as a carrier gas and introducing external air; And (ii) pyrolyzing the sprayed precursor solution at 600 to 1,200 ° C. to form a catalyst powder.
  • the precursor solution may be sprayed into the reactor and converted into finer droplets in order to control the particle diameter, the apparent density, etc. of the catalyst powder.
  • the pressure can be adjusted in the range of 2 to 5 atm.
  • the spray pressure is less than 2 atm, the particle size, apparent density, etc. of the catalyst powder may not be controlled within a predetermined range, thereby lowering the purity of the carbon nanotubes synthesized therethrough.
  • the spray pressure is more than 5 atm, the particle size of the droplets is excessively small, so that the catalysts obtained may aggregate with each other.
  • the droplet size can be more precisely controlled, and thus the particle size and apparent density of the catalyst powder can be precisely controlled.
  • droplets may be formed by spraying a gas simultaneously with spraying the precursor solution, or spray droplets may be formed by spraying a gas after spraying the precursor solution.
  • the method of preparing the catalyst powder may include spraying the gas into the reactor before the step (ii). It may further include.
  • gas air, nitrogen, argon or a mixed gas of two or more thereof may be used, and preferably air may be used.
  • electrostatic attraction may be added to the gas spray to improve the efficiency of the droplet formation.
  • the pressure of the spraying gas can be adjusted within the range of 2 to 5 atmospheres, and the effect of the case out of the above range is described above. It's like that.
  • the catalyst powder may be finally prepared by heating the droplet to evaporate the solvent and decomposing the precursor.
  • the temperature of the reactor may be 600 ⁇ 1,200 °C, preferably, 700 ⁇ 900 °C.
  • the temperature of the reactor is less than 600 °C, the dry state of the catalyst powder is poor, an additional process is required, which is disadvantageous in terms of economics, through which the purity or physical properties of the carbon nanotubes manufactured may be reduced.
  • the temperature of the reactor is more than 1,200 °C excessive cost to build equipment or equipment not only causes economic losses, but also the performance of the catalyst may be degraded due to the formation of solid solution or modification of the crystal structure.
  • the catalyst powder may be introduced into a fluidized bed reactor heated to 600 to 900 ° C., and a carbon-based gas and a carrier gas may be injected to synthesize multi-walled carbon nanotubes from the catalyst powder.
  • step (c) heating the fluidized bed reactor to 600 ⁇ 900 °C; (ii) feeding catalyst powder at the top of the reactor and fluidizing in the reactor; (iii) supplying a carbonaceous gas and a carrier gas through a rotary blade at the bottom of the reactor; And (iv) thermally vapor-depositing carbon on the catalyst powder fluidized by an upward air flow by the rotary blades.
  • the steps (a) to (c) may be carried out continuously, and in particular, the catalyst powder prepared by spray pyrolysis in the steps (a) to (b) may be carried out in a fluidized bed reactor for producing carbon nanotubes. Continuously added, a large amount of carbon nanotubes can be effectively produced.
  • the catalyst powder may be used in a gas phase synthesis method for synthesizing carbon nanotubes, wherein Ma is at least two metals selected from Fe, Ni, Co, Mn, Cr, Mo, V, W, Sn, and Cu, and the Mb Is at least one metal selected from Mg, Al, Si and Zr, and therefore may include at least three or more metals, preferably three to five metal components.
  • the Ma is a catalyst component and an active ingredient in the catalyst powder, compared to the case of using a single metal component as the catalyst component and the active ingredient, by mixing two or more metal components during the carbon nanotube synthesis process Impurity can be suppressed to improve purity.
  • catalyst component refers to a substance that substantially lowers the chemical reaction energy of the substance, i.e., the main catalyst
  • active component refers to a substance that aids in the action of the catalyst component, i.e., a promoter. it means.
  • the catalyst component and the active component have a uniform distribution within a certain range, the synthesis yield of carbon nanotubes may be improved.
  • the mole fractions x and y of Ma and Mb may satisfy a relationship of 2.0 ⁇ x ⁇ 7.5 and 2.5 ⁇ y ⁇ 8.0, respectively. If x is less than 2.0, the activity of the catalyst and the resulting synthesis yield of carbon nanotubes may be reduced. If the content is greater than 7.5, the content of Mb, which is a support component, is relatively low, thus reducing the durability of the catalyst powder. There is a problem that is difficult to apply to the continuous fluidized bed chemical vapor deposition method for production.
  • the catalyst powder may have a hollow structure having a thickness of 0.5 to 10 ⁇ m, preferably 1 to 8 ⁇ m, and the hollow ratio may be 50% by volume or more.
  • the apparent density of the catalyst powder may be 0.05 ⁇ 0.70 g / mL.
  • the term “hollow structure” refers to a three-dimensional structure with an empty interior, for example, a spherical or polyhedral structure with an empty interior, wherein the hollow structure is a closed structure in which the entire hollow is closed. ), Some of the hollows may be interpreted to include an open structure, or a combination thereof.
  • the apparent density is higher than about 0.7 g / mL, making it difficult to apply to continuous fluidized bed chemical vapor deposition for mass production of carbon nanotubes, and only to the outer surface of the catalyst powder.
  • carbon nanotubes grow, there is a problem that it is difficult to improve the yield to a certain level or more.
  • the catalyst powder has a hollow structure
  • the apparent density is lower than that of the conventional catalyst powder, so that the catalyst powder can be applied to a continuous fluidized bed chemical vapor deposition method, and carbon nanotubes are directed outward from the outer surface of the hollow structure. Not only can it grow, it can also grow inward from the inner surface of the hollow structure can significantly improve the carbon nanotube synthesis yield.
  • the conversion rate of the carbon-based gas according to Equation 2 may be 80% or more.
  • Conversion rate (%) ⁇ (weight of multi-walled carbon nanotubes (g))-(weight of catalyst powder (g)) ⁇ / ⁇ (carbon-based gas supply (L)) * (of carbon in 1 mol of carbon-based gas) Weight (g / mol)) / (22.4 (L / mol)) ⁇ * 100
  • the carbon-based gas may be, for example, one selected from the group consisting of saturated or unsaturated hydrocarbons having 1 to 4 carbon atoms, carbon monoxide, benzene, and mixtures of two or more thereof, and preferably, may be ethylene gas. It is not limited to this.
  • the carrier gas may be, for example, one selected from the group consisting of helium, nitrogen, argon, and a mixture of two or more thereof, and preferably, nitrogen, but is not limited thereto.
  • Step (d) recovering the multi-walled carbon nanotubes from the fluidized bed reactor; may further include.
  • Step (d) may include: (i) transferring the multi-walled carbon nanotubes to a cyclone using nitrogen gas; And (ii) screening the multi-walled carbon nanotubes by removing impurities from the multi-walled carbon nanotubes in the cyclone.
  • cyclone refers to a device that separates impurities contained in a certain mixture, and when a mixture containing impurities flows in the tangential direction of the upper circumference of the conical device, a high-speed swirl flow occurs.
  • the impurity in the mixture impinges on the wall and is discharged and removed to the bottom of the apparatus while the kinetic energy is reduced, and the mixture from which the impurity is removed is discharged to the top.
  • the aggregated carbon nanotubes which is a kind of impurities, are discharged and removed to the lower end of the cyclone, and the purified multi-walled carbon nanotubes are discharged through the upper end of the cyclone to pass through the packaging device located at the rear end of the high purity. Uniform products can be produced.
  • the multi-walled carbon nanotubes may be aggregated to exist as bundle-type carbon nanotubes.
  • the bundle type carbon nanotubes may basically exist in a form in which a plurality of carbon nanotubes, preferably, a plurality of multi-walled carbon nanotubes are aggregated with each other.
  • Each carbon nanotube and the aggregate thereof may be straight, curved, or a mixture thereof.
  • An average bundle diameter of the bundled carbon nanotubes may be 0.5 to 20 ⁇ m, and an average bundle length may be 10 to 200 ⁇ m.
  • the Raman spectral intensity ratio (I G / I D ) of the multi-walled carbon nanotubes may be 0.7 ⁇ 1.5, the average diameter may be 5 ⁇ 50nm, the apparent density may be 0.01 ⁇ 0.07g / mL. .
  • the catalyst of Comparative Example 5 is the same in composition and composition as the catalyst of Example 5, but the catalyst is prepared by spray drying, and Example 5 is different from the method of preparing the catalyst. Specifically, in the case of Comparative Example 5 compared to the spray pyrolysis method of Example 5 to prepare a catalyst powder by spraying the precursor solution in the reactor at a temperature of 200 °C relatively low, 700 °C, 1 hour in an air atmosphere heat treatment furnace The solid catalyst powder of the solid shape was prepared by heat treatment for a while.
  • the catalysts of Comparative Examples 6 and 7 were prepared by the co-precipitation method and the combustion method, respectively, and they each had a plate shape as shown in FIG.
  • the catalyst of Comparative Example 8 is a catalyst prepared using alumina (Al 2 O 3 ) powder which is not dissolved in water as a precursor of Al in the catalyst component.
  • Carbon nanotubes were synthesized using the catalyst powder. Specifically, each catalyst powder was introduced into a fluidized bed chemical vapor deposition reactor having a diameter of 350 mm, and maintained at 700-800 ° C. in a nitrogen atmosphere. Thereafter, a mixture of nitrogen and ethylene was supplied at a rate of 150 L per minute for 40 minutes to synthesize carbon nanotubes grown on the respective catalyst powders.
  • the apparent density of the catalyst powder was obtained by measuring the weight by filling the catalyst powder in the mass cylinder, and dividing the measured weight by the volume of the mass cylinder.
  • the apparent density of the carbon nanotubes was measured in the same manner.
  • the synthesis yield of carbon nanotubes was calculated according to the formula "Weight of synthesized carbon nanotubes (g)] / [weight of injected catalyst powder (g)] * 100", and the conversion of ethylene was " ⁇ (multiple Weight of wall carbon nanotubes (g))-(weight of catalyst powder (g)) ⁇ / ⁇ (carbon-based gas supply (L)) * (weight of carbon in 1 mol of carbon-based gas (g / mol)) / (22.4 (L / mol)) ⁇ * 100 ".
  • the measurement results are shown in Table 2 below.
  • Example 1 0.180 1,264 85.7 0.015
  • Example 2 0.060 1,490 90.1 0.022
  • Example 3 0.516 1,400 89.7 0.020
  • Example 4 0.077 1,354 91.2 0.020
  • Example 5 0.072 1,437 93.5 0.022
  • Example 6 0.084 2,600 83.6 0.023
  • Example 7 0.090 1,392 91.4 0.015
  • Example 8 0.215 4,282 93.5 0.027
  • Example 10 0.662 4,030 95.6 0.034
  • Comparative Example 1 0.164 651 68.5 0.008
  • Comparative Example 2 0.470 967 78.6 0.029
  • Comparative Example 3 0.437 826 74.8 0.076 Comparative Example 4 0.906 0 0 - Comparative Example 5 0.815 763 72.3 0.053 Comparative Example 6 0.726 582
  • the catalysts of Comparative Examples 4, 5, 6, and 8 are difficult to float in the fluidized bed chemical vapor deposition method of synthesizing carbon nanotubes while floating the catalyst powder with the reaction gas with an apparent density of 0.70 g / mL or more. there is a problem.

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  • Organic Chemistry (AREA)
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Abstract

La présente invention concerne, dans un mode de réalisation, un procédé de fabrication de nanotubes de carbone à parois multiples, le procédé comprenant les étapes consistant à : (a) dissoudre un précurseur de métal dans un solvant pour préparer une solution de précurseur; (b) effectuer une décomposition thermique tout en pulvérisant la solution de précurseur dans un réacteur, formant ainsi une poudre de catalyseur; et (c) introduire la poudre de catalyseur dans un réacteur à lit fluidisé chauffé entre 600 °C et 900 °C et pulvériser un gaz à base de carbone et un gaz vecteur pour synthétiser des nanotubes de carbone à parois multiples à partir de la poudre de catalyseur, les étapes (a) à (c) étant effectuées en continu et la poudre de catalyseur contenant des composants métalliques selon l'équation 1 ci-dessous. <Équation 1> Ma:Mb = x:y, Ma représentant au moins deux métaux choisis parmi Fe, Ni, Co, Mn, Cr, Mo, V, W, Sn et Cu; Mb représentant au moins un métal choisi parmi Mg, Al, Si et Zr; x et y représentant chacun le rapport molaire Ma et Mb; et x+y = 10, 2,0≤x≤7,5 et 2,5≤y≤8,0.
PCT/KR2018/002548 2017-03-03 2018-03-02 Procédé de fabrication de nanotubes de carbone à parois multiples à l'aide d'un processus de type continu Ceased WO2018160041A1 (fr)

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JP2019548043A JP6872627B2 (ja) 2017-03-03 2018-03-02 連続式工程を利用した多重壁カーボンナノチューブの製造方法
CN201880023603.XA CN110494390A (zh) 2017-03-03 2018-03-02 使用连续式工序的多壁碳纳米管的制备方法
US16/490,772 US11117803B2 (en) 2017-03-03 2018-03-02 Method for manufacturing multi-wall carbon nanotubes using continuous type process

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118239477A (zh) * 2024-04-10 2024-06-25 南通捷鉴智能数字科技有限公司 一种智能穿戴用高导电碳纳米管粉体材料的制备方法

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US20080206125A1 (en) * 2005-09-20 2008-08-28 Nanocyl S.A. Catalyst System for a Multi-Walled Carbon Nanotube Production Process
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