WO2015047050A1 - Catalyseur pour produire des nanotubes de carbone et nanotubes de carbone produits au moyen de celui-ci - Google Patents

Catalyseur pour produire des nanotubes de carbone et nanotubes de carbone produits au moyen de celui-ci Download PDF

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WO2015047050A1
WO2015047050A1 PCT/KR2014/009235 KR2014009235W WO2015047050A1 WO 2015047050 A1 WO2015047050 A1 WO 2015047050A1 KR 2014009235 W KR2014009235 W KR 2014009235W WO 2015047050 A1 WO2015047050 A1 WO 2015047050A1
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catalyst
carbon nanotubes
carbon nanotube
surface area
specific surface
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PCT/KR2014/009235
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English (en)
Korean (ko)
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김성진
조동현
강경연
손승용
차진명
장형식
이승용
우지희
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주식회사 엘지화학
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Priority claimed from KR20140129449A external-priority patent/KR101508101B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP14848695.4A priority Critical patent/EP3053878A4/fr
Priority to CN201480003906.7A priority patent/CN104884384B/zh
Priority to JP2015545399A priority patent/JP6131516B2/ja
Priority to US14/439,168 priority patent/US9956546B2/en
Publication of WO2015047050A1 publication Critical patent/WO2015047050A1/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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • B01J23/8472—Vanadium
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/881—Molybdenum and 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
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/882—Molybdenum and cobalt
    • 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 catalyst for producing carbon nanotubes, particularly a catalyst capable of producing carbon nanotubes having a high specific surface area, and a carbon nanotube prepared using the same.
  • Carbon nanostructures refers to nanoscale carbon nanostructures having various shapes such as nanotubes, nanohairs, fullerenes, nanocones, nanohorns, and nanorods. High utilization in the technical field.
  • carbon nanotubes is a material in which the carbon atoms arranged in a hexagonal shape in the form of a tube, the diameter is approximately 1 to 100 nm.
  • CNTs carbon nanotubes
  • Such CNTs exhibit non-conductor, conductor or semiconducting properties depending on their unique chirality, and the carbon atoms are connected by strong covalent bonds, resulting in approximately 100 times greater tensile strength than steel, and excellent flexibility and elasticity. It is also chemically stable.
  • the type of CNT includes a single-walled carbon nanotube (SWCNT) composed of one layer and a diameter of about 1 nm, and a double-walled carbon composed of two layers and a diameter of about 1.4 to 3 nm.
  • nanotubes, DWCNTs) and multi-walled carbon nanotubes (MWCNTs) having a diameter of about 5 to 100 nm and consisting of three or more layers.
  • CNTs Due to characteristics such as chemical stability, excellent flexibility and elasticity, CNTs are being commercialized and applied in various fields, such as aerospace, fuel cells, composites, biotechnology, medicine, electrical and electronics, and semiconductors.
  • the primary structure of the CNT has a limit in directly adjusting its diameter or length to actual specifications for industrial applications, and thus, despite the excellent properties of the CNT, there are many limitations in industrial applications or applications.
  • the CNT is generally manufactured by arc discharge, laser ablation, chemical vapor deposition, or the like.
  • the arc discharge method and the laser evaporation method are difficult to mass-produce, and excessive arc production cost or laser equipment purchase cost is a problem.
  • the chemical vapor deposition method has a problem that the synthesis rate is very slow in the case of using a gas phase dispersion catalyst and the particles of the synthesized CNT are too small. There is a limit to mass production. Therefore, in order to increase the yield of CNT in chemical vapor deposition, studies on catalysts, reaction conditions, and the like are continuing.
  • CNTs having a small diameter and a form that can be well dispersed and mixed during compounding are required.
  • the problem to be solved by the present invention is to provide a catalyst having a small diameter and a high specific surface area, CNT having a bundle structure that can be dispersed and mixed well when compounding with a polymer in high yield. It is.
  • Another object of the present invention is to provide a CNT aggregate produced using the catalyst.
  • Another object of the present invention to provide a conductive polymer composite containing the CNT aggregate.
  • the support is supported by a graphitized metal catalyst and has a maximum diffraction peak at 2 ⁇ values of 35 to 38 ° in an XRD pattern in the range of 10 ° to 80 ° and at a value of 17 ° to 22 ° for the maximum diffraction peak size (a).
  • a catalyst for producing carbon nanotubes in which the ratio (b / a) of the size (b) of the diffraction peak of is 0.08 or more.
  • the XRD pattern of the catalyst may further have one or more diffraction peaks selected from 2 ⁇ values 30-33 °, 43-46 °, 57-60 ° and 63-67 °.
  • the catalyst may have a crystal size of 3 to 50 nm.
  • the catalyst is a supported catalyst obtained by calcining aluminum hydroxide at a first firing temperature of 100 to 500 ° C. to form a support, and carrying a catalyst metal precursor on the support and then firing at a second firing temperature of 100 to 800 ° C. Can be.
  • the catalyst may be selected to have a particle size of 30 to 150 ⁇ m and a number average particle size of 40 to 80 ⁇ m.
  • the graphitized metal catalyst is nickel (Ni), cobalt (Co), iron (Fe), platinum (Pt), gold (Au), aluminum (Al), chromium (Cr), copper (Cu), magnesium (Mg) , Manganese (Mn), molybdenum (Mo), rhodium (Rh), silicon (Si), tantalum (Ta), titanium (Ti), tungsten (W), uranium (U), vanadium (V) and zirconium (Zr) It may be one or more metals or alloys selected from the group consisting of.
  • the graphitized metal catalyst may be a plural-based metal catalyst including a main catalyst-catalyst.
  • the main catalyst may be at least one selected from Co and Fe, and the cocatalyst may be at least one selected from Mo and V.
  • the graphitized metal catalyst may be a binary metal catalyst selected from Co / Mo, Co / V, Fe / Mo, and Fe / V.
  • the graphitized metal catalyst may have a content of 0.5 to 5 mol of the cocatalyst with respect to 10 mol of the main catalyst.
  • the graphitized metal catalyst may be 5 to 40 parts by weight based on 100 parts by weight of the catalyst.
  • the present invention also provides a carbon nanotube aggregate comprising carbon nanotubes grown on the catalyst described above, wherein the BET specific surface area of the carbon nanotube aggregate is 200 m 2 / g or more, and the BET specific surface area and the crystal of the catalyst are determined.
  • carbon nanotube aggregates whose sizes satisfy the following relationship:
  • y is the BET specific surface area (m 2 / g) and x is the crystal size (nm) of the catalyst.
  • the specific surface area of the carbon nanotube aggregate and the crystal size of the catalyst may satisfy the following relationship.
  • the present invention also provides a method for producing a carbon nanotube aggregate comprising the step of contacting the catalyst described above with a gaseous carbon source to form carbon nanotubes (CNTs).
  • the gaseous carbon source may be at least one selected from the group consisting of carbon monoxide, methane, ethane, ethylene, ethanol, acetylene, propane, propylene, butane, butadiene, pentane, pentene, cyclopentadiene, hexane, cyclohexane, benzene and toluene have.
  • the reaction temperature may be 600 to 750 °C.
  • the present invention also provides a composite material comprising the carbon nanotube aggregate.
  • the composite material may have a conductivity that is inversely proportional to the crystal size of the catalyst.
  • the present invention since a carbon nanotube (CNT) having a large specific surface area and having a shape that can be well dispersed and mixed can be obtained, it is possible to improve physical properties of the composite material including the CNT. As a result, the CNTs according to the present invention can be usefully used in various fields such as energy materials, functional composites, medicines, batteries, semiconductors, and display devices.
  • CNT carbon nanotube
  • 1 is an XRD pattern of a catalyst prepared in an embodiment of the present invention.
  • Figure 2 is a graph showing the correlation between the crystal size of the catalyst prepared in the embodiment of the present invention and the BET specific surface area of the CNT aggregate prepared using the same.
  • FIG 3 is an SEM image of a CNT aggregate prepared according to an embodiment of the present invention.
  • FIG 4 is a graph showing the surface resistance of the polymer composite containing the CNT aggregate prepared according to the embodiment of the present invention as a correlation with the crystal size of the catalyst used to prepare the CNT aggregate.
  • the present invention obtains a supported catalyst having a controlled crystal size by optimizing a pretreatment step of a support and a formation step of a supported catalyst, and by using the same, a CNT aggregate having a low diameter and high specific surface area, and a polymer having conductivity controlled by containing such CNT aggregate It relates to manufacturing a composite material.
  • the catalyst according to the present invention has a graphitized metal catalyst on a support, has a maximum diffraction peak at a 2 ⁇ value of 35 to 38 ° in an XRD pattern in a range of 10 ° to 80 °, and has a maximum diffraction peak size (a).
  • the ratio (b / a) of the magnitude (b) of the diffraction peak at the 2 ⁇ value of 17 to 22 ° is characterized by being 0.08 or more.
  • the b / a may be 0.15 or less, 0.09 to 0.15, or 0.09 to 0.13.
  • the catalyst according to one embodiment may further have one or more diffraction peaks selected from 2 ⁇ values 30-33 °, 43-46 °, 57-60 ° and 63-67 ° of the XRD pattern. Can be.
  • the diffraction peak at 2 ⁇ values 30 to 33 ° may have a size of 0.3 to 0.5, or 0.35 to 0.45 relative to the maximum diffraction peak.
  • the diffraction peak at 2 ⁇ values 43 to 46 ° may have a size of 0.1 to 0.3, or 0.15 to 0.25 with respect to the maximum diffraction peak.
  • the diffraction peak at 2 ⁇ values 57 to 60 ° may have a size of 0.1 to 0.25, or 0.15 to 0.22 relative to the maximum diffraction peak.
  • the diffraction peak at the 2 ⁇ value of 63 to 67 ° may have a size of 0.3 to 0.5, or 0.35 to 0.45 relative to the maximum diffraction peak.
  • the catalyst can be controlled in the crystal size range of 3 to 50 nm, or 10nm to 50nm, the crystal size of the catalyst is the calcination conditions of the catalyst, that is, the type of catalyst metal, catalyst metal loading, calcining amount, firing time, firing temperature It can be controlled by adjusting various conditions.
  • the 'crystal size' of the catalyst is also referred to as 'crystallite size', and is calculated from the broadening of peaks appearing according to the XRD measurement. More specifically, the Bragg-Brentano method, a mode of incidence angle 1/2 of 2theta, is used, and the grain size formula is applied to the full pattern fitting method using the fundamental approach in the Bruker TOPAS program. Calculated by Therefore, it should be distinguished from the 'catalyst particle size' or the 'catalyst particle size' obtained from the SEM photograph. Since the grain size measurement and calculation method is in accordance with known standard methods, detailed description is omitted.
  • the catalyst according to the present invention exhibits a tendency to decrease the BET specific surface area of the resulting CNT aggregate as the crystal size of the catalyst increases.
  • the CNT aggregate produced using the catalyst according to the present invention has a BET specific surface area of 200 m 2 / g or more, and the BET specific surface area and crystal size of the catalyst satisfy the following relation:
  • y is the BET specific surface area (m 2 / g) and x is the crystal size (nm) of the catalyst.
  • the specific surface area of the carbon nanotube aggregate and the crystal size of the catalyst may satisfy one or more of the following relational expressions.
  • the specific surface area used in the present invention is measured by the BET method. Specifically, the specific surface area used is calculated by calculating the amount of nitrogen gas adsorption under liquid nitrogen temperature (77K) using BEL Japan's BELSORP-mini II. .
  • CNT aggregates according to the invention have a BET specific surface area of from 200 to 500 m 2 / g, or from 200 to 300 m 2 / g, or from 300 to 500 m 2 / g, or from 300 to 400 m 2 / g, or from 200 to 400 m 2 / g.
  • the electrical conductivity of the polymer compound containing the same tends to be improved.
  • the conductivity of the CNT-containing polymer compound is believed to be influenced by physical properties such as diameter and crystallinity of the CNT aggregate and dispersibility (associated with the CNT shape) during compounding.
  • the crystallite size of the catalyst according to the present invention and the surface resistance of the polymer compound containing the CNT aggregate prepared using the same have a relationship as shown in FIG. 4.
  • the crystal size of the catalyst is controlled to be small, a CNT aggregate having a high specific surface area (low diameter) can be produced, and as a result, a polymer compound having excellent conductivity can be prepared.
  • the support precursor obtained by first firing at a first firing temperature for example, at a temperature of 100 ° C. to 500 ° C. is loaded with a graphitization catalyst, and then, it is 100 ° C. to 800 ° C.
  • a supported catalyst prepared by second firing at a temperature is prepared.
  • the supported catalyst may be contacted with a gaseous carbon source to prepare a bundle of carbon nanotube aggregates having a BET specific surface area of preferably 200 m 2 / g or more (see FIG. 3).
  • 'bundle type' refers to a secondary shape in the form of a bundle or a rope, in which a plurality of CNTs are arranged or intertwined side by side, unless otherwise stated.
  • 'Non-bundle or entangled type' means a shape without a certain shape, such as a bundle or a rope shape.
  • the support precursor used in the production method serves to support the graphitization catalyst, it is possible to control the shape of the CNT according to the type.
  • an aluminum-based support precursor preferably aluminum hydroxide (aluminum-tri-hydroxide, ATH) can be used.
  • a support precursor can be used by drying for 1 hour to 24 hours at 50 °C to 150 °C.
  • the first firing temperature is preferably 500 ° C. or less, much lower than 700 ° C., which is known to convert aluminum hydroxide to alumina. That is, the first firing may include a heat treatment process performed at a temperature of about 100 ° C to about 500 ° C, or about 120 ° C to about 450 ° C, or 200 to 450 ° C, or 300 to 450 ° C, or 200 to 400 ° C. Can be.
  • the aluminum-based support formed by the above process preferably contains 30 wt% or more of AlO (OH) converted from Al (OH) 3 and does not include Al 2 O 3 .
  • the aluminum (Al) -based support may further include one or more selected from the group consisting of ZrO 2 , MgO and SiO 2 .
  • the aluminum (Al) -based support may have a spherical or potato shape, and may have a porous structure, a molecular sieve structure, a honeycomb structure, or another suitable structure to have a relatively high surface area per unit mass or volume.
  • the support precursor may have a primary particle size of about 20 to about 200 ⁇ m, porosity of about 0.1 to about 1.0 cm 3 / g, specific surface area of less than about 1 m 2 / g.
  • the first firing process may be performed for about 0.5 hours to about 10 hours, preferably about 1 hour to 5 hours, but is not limited thereto.
  • CNTs Contacting the graphitization catalyst used in the preparation method with a gaseous carbon source can form CNTs.
  • the growth process of CNTs is described above.
  • the carbonaceous material which is a gaseous carbon source
  • the graphite catalyst for example, a graphite metal catalyst
  • the carbonaceous material is thermally decomposed on the surface of the metal catalyst.
  • CNTs in which the carbon atom generated from the decomposed carbon-containing gas penetrates into the graphitized metal catalyst to be dissolved and then exceeds the solubility limit which is an inherent property of the graphitized metal catalyst.
  • the nucleation of the furnace occurs and grows into CNTs.
  • the graphitized metal catalyst serves to help the carbon components present in the carbonaceous material combine with each other to form a hexagonal ring structure, for example, to synthesize graphite, induce carbonization, or CNT It is possible to use the catalyst used to prepare the. More specifically, nickel (Ni), cobalt (Co), iron (Fe), platinum (Pt), gold (Au), aluminum (Al), chromium (Cr), copper (Cu), magnesium (Mg), With manganese (Mn), molybdenum (Mo), rhodium (Rh), silicon (Si), tantalum (Ta), titanium (Ti), tungsten (W), uranium (U), vanadium (V) and zirconium (Zr) One or more metals or alloys selected from the group consisting of can be used.
  • the graphitization catalyst may use a binary or ternary or higher polyvalent metal.
  • a binary or multi-part graphitization catalyst may be composed of a main catalyst and a promoter, Co, Fe, Ni, etc. may be used as the main catalyst, Mo, V, etc. may be used as the promoter.
  • Such binary or plural graphitization catalysts are Co / Mo, Co / V, Fe / Mo, Fe / V, Fe / Co, Fe / Co / V, Fe / Co / Mo, Co / Mo / V, Fe / Mo / V, Fe / Co / Mo / V, etc. are mentioned. Among these, it is more preferable that Co and V are included.
  • the component ratio thereof may be, for example, 0.1 to 10 moles or 0.5 to 5 moles of the cocatalyst based on 10 moles of the main catalyst.
  • the graphitization catalyst is supported on the support in the form of various precursors such as metal salts, metal oxides, or metal compounds.
  • various precursors such as metal salts, metal oxides, or metal compounds.
  • Fe salt, Fe oxide, Fe compound, Ni salt, Ni oxide, Ni compound, Co salt, Co oxide, Co compound, Mo oxide, Mo compound, Mo salt, V oxide, V compound, V salt, etc. can be illustrated.
  • Fe (NO 3 ) 2 ⁇ 6H 2 O, Fe (NO 3 ) 2 ⁇ 9H 2 O, Fe (NO 3 ) 3 , Fe (OAc) 2 , Ni (NO 3 ) 2 ⁇ 6H 2 O, Co (NO 3 ) 2 .6H 2 O, Co 2 (CO) 8 , [Co 2 (CO) 6 (t-BuC CH)], Co (OAc) 2 , (NH 4 ) 6 Mo 7 O 24 4H 2 O, Mo (CO) 6 , (NH 4 ) MoS 4 , NH 4 VO 3 , and the like can be used.
  • the precursor of the graphitization catalyst When the precursor of the graphitization catalyst is supported on the support in the form of a solution, and then undergoes a second firing process, it is mainly supported in the form of a metal oxide to form a supported catalyst.
  • a support for example a granular aluminum-based support in the precursor aqueous solution of the graphitization catalyst
  • the mixture is calcined at a first firing temperature of about 100 to 500 ° C. to form a support, and a catalyst metal precursor is supported on the support and then calcined at a second firing temperature of 100 to 800 ° C. to support CNT production catalyst.
  • It can be prepared by a method comprising; obtaining a.
  • the vacuum drying may be carried out by rotary evaporation in the range of about 30 minutes to about 12 hours under vacuum in the temperature range of about 40 to about 100 °C.
  • the method may include aging by rotation or stirring at about 45 to about 80 ° C. before the vacuum drying. For example, it may be performed for up to 5 hours, 20 minutes to 5 hours, or 1 to 4 hours.
  • the second firing process for forming the supported catalyst may be performed at a temperature of about 100 ° C to about 800 ° C, for example, about 200 ° C to about 800 ° C or 550 ° C to about 800 ° C. It is preferable that the temperature of a 2nd baking process is 200-400 degreeC higher than the temperature of a 1st baking process.
  • the particle size or average particle diameter measured before the second firing of the supported catalyst used in the preparation method is about 30 ⁇ m to about 150 ⁇ m, and the primary particle diameter of the granular support and the graphitization catalyst is about 10 nm to about 50 nm.
  • the spherical or potato shape refers to a three-dimensional shape such as a spherical and ellipsoidal shape having an aspect ratio of 1.2 or less.
  • the supported catalyst when preparing a CNT according to the present invention using a fluidized bed reactor, in particular, has a particle diameter of about 30 ⁇ m to about 150 ⁇ m, a number average particle diameter (Mn) of 40 to 80 ⁇ m, or It can be used selectively to be 50 to 70 ⁇ m, or 50 to 70 ⁇ m. This is because it is important to ensure that the catalyst fluidized bed flows well without catalyst aggregation in the reaction zone in the fluidized bed reactor.
  • Mn number average particle diameter
  • the supported catalyst may include about 5 to about 40 parts by weight of the graphitization catalyst based on 100 parts by weight of the supported catalyst, but is not limited thereto.
  • the supported catalyst includes a Co-based graphitization catalyst
  • the content of Co may be about 3 to about 100 moles based on 100 moles of the support.
  • the graphitization catalyst may have a structure in which one or more layers are coated on the surface and pores of the granular support, preferably the aluminum-based support.
  • a supported catalyst using an impregnation method, in which the bulk density of the catalyst itself is higher than that of the coprecipitation catalyst and less than 10 microns, unlike the coprecipitation catalyst, when the supported catalyst is used. It is possible to reduce the possibility of fine powder due to attrition, which can occur during fluidization process because of the small amount of fine powder. Also, the mechanical strength of the catalyst itself is excellent, which makes it possible to stabilize the reactor operation.
  • CNTs may be prepared by growing CNTs by chemical vapor phase synthesis through decomposition of a carbon source using the supported catalyst as described above.
  • the CNT in the method for producing CNTs according to the chemical vapor phase synthesis method, after charging the graphitization catalyst in the reactor, the CNT can be prepared by supplying a gaseous carbon source under conditions of normal pressure and high temperature.
  • the growth of the CNTs is carried out by the process of infiltrating and saturating the pyrolyzed hydrocarbons by applying high temperature heat to the graphitization catalyst, and depositing carbons from the saturated graphitization catalyst to form a hexagonal ring structure.
  • the chemical vapor phase synthesis method is to add the supported catalyst to a horizontal fixed bed reactor or fluidized bed reactor and about 500 °C to about 900 °C, or about 500 °C to 800 °C, or about 600 °C to 800 °C, about 600 °C
  • One or more carbon sources selected from saturated or unsaturated hydrocarbons having 1 to 6 carbon atoms at a temperature of from about 750 ° C., or about 650 ° C. to about 700 ° C., or the carbon source with a reducing gas (eg, hydrogen) and a carrier gas ( For example, it may be carried out by injecting a mixed gas of nitrogen). Injecting a carbon source into the supported catalyst to grow the CNTs may be performed for 30 minutes to 8 hours.
  • the supply gas may be a carbon source and a reducing gas or a carrier gas, respectively, or a mixture thereof.
  • induction heating radiant heat, laser, IR, microwave, plasma, UV, surface plasmon heating, etc. can be used without limitation.
  • the carbon source used in the chemical vapor phase synthesis method may supply carbon, and any material that may exist in the gas phase at a temperature of 300 ° C. or higher may be used without particular limitation.
  • a gaseous carbonaceous substance any compound containing carbon may be used, and a compound having 6 or less carbon atoms is preferable, and more preferably a compound having 4 or less carbon atoms.
  • one or more selected from the group consisting of carbon monoxide, methane, ethane, ethylene, ethanol, acetylene, propane, propylene, butane, butadiene, pentane, pentene, cyclopentadiene, hexane, cyclohexane, benzene and toluene can be used. It is not limited.
  • the mixed gas of hydrogen and nitrogen transports the carbon source, prevents CNTs from burning at high temperatures, and assists in the decomposition of the carbon source.
  • Such gaseous carbon source, hydrogen and nitrogen can be used in various volume ratios, for example, the volume ratio of nitrogen: gaseous carbon source: hydrogen is 1: 0.1 to 10: 0 to 10, or 1: 0.5 to 1.5: 0.5 to 1.5 Can be used in the range of.
  • the flow rate of the reaction gas can be suitably used in the range of about 100 sccm or more and about 10,000 sccm or less.
  • the CNTs are subjected to a cooling process.
  • the CNTs may be arranged more regularly by the cooling process.
  • Such cooling process may be natural cooling (removal of heat source), or cooling at a rate of about 5 ° C. to about 30 ° C. per minute.
  • a bundle type CNT having a BET specific surface area of about 200 m 2 / g or more, preferably about 200 m 2 / g to about 500 m 2 / g can be obtained.
  • the specific surface area can be measured by a conventional BET method.
  • the production method is capable of obtaining CNTs in high yield, for example, achieving a yield of about 5 to 50 times, or about 10 to 40 times.
  • the yield is obtained from the synthesized carbon nanotubes at room temperature and its content can be measured using an electronic balance.
  • the reaction yield can be calculated based on the weight of the supported catalyst used and the weight increase after the reaction based on the following formula.
  • the CNTs may be in a bundle having a flatness of about 0.9 to about 1, and as the BET specific surface area increases, each CNT strand diameter is about 2 nm to about 20 nm, preferably about 3 nm to about 8 nm. It may have a low diameter.
  • the flatness may be defined by the following equation.
  • CNTs have a large BET specific surface area, that is, a low diameter, and have a bundle shape, so that the CNTs are well dispersed and mixed in other materials, for example, polymers, thereby improving physical properties when forming a composite material.
  • Electrode structures such as solar cells, fuel cells, lithium batteries and supercapacitors; Functional composite materials; Energy material; medicine; It can be usefully used for semiconductors such as FETs.
  • Co-V metal catalyst was prepared as a graphitization catalyst.
  • Citric acid was added to Flask A in which NH 4 VO 3 was dissolved in 20 ml water as the precursor material of V.
  • Co (NO 3 ) 2 .6H 2 O was added as a precursor material of Co so that the molar ratio of Co: V was 10: 1.
  • the prepared aqueous metal solution was observed as a clear solution without precipitation.
  • the prepared catalyst was analyzed by XRD and the crystal size was measured.
  • the XRD analysis equipment used was as follows.
  • LynxEye position sensitive detector (3.7 ° slit)
  • the crystal size of the catalyst according to Co content and firing temperature is shown in Table 2. The crystal size was obtained by full pattern fitting.
  • CNT synthesis was tested in a laboratory scale fluidized bed reactor using each of the supported catalysts for synthesizing CNTs prepared above.
  • the catalyst for synthesizing CNT prepared in D was heated in a quartz tube reactor having an inner diameter of 58 mm and a length of 1200 mm, heated to 675 ° C. in a nitrogen atmosphere, and then maintained with a volume mixing ratio of nitrogen, hydrogen, and ethylene gas.
  • a predetermined amount of CNT aggregates were synthesized by synthesizing for 5.5 hours at 5.5: 1: 1 with a total of 4000 ml per minute.
  • the specific surface area and yield of the obtained CNT aggregate are shown in Table 3.
  • the specific surface area was measured by the BET method, and specifically, it calculated by calculating
  • FIG. 3 is an SEM image of a CNT aggregate. It can be seen from FIG. 3 that a bundled CNT aggregate is formed.
  • melt extrusion was carried out at 240 ⁇ 280 °C using a twin screw extruder to prepare a compound in the form of pellets.
  • the conductivity was measured using a conductivity meter (SRM-110, PINION). The relationship of the surface resistance of the polymer composite according to the catalyst crystal size is shown in FIG. 4.
  • the specific surface area of the CNT aggregate and the conductivity of the polymer composite including the CNT aggregate can be controlled by controlling the crystal size of the catalyst when preparing the supported catalyst.
  • the present invention since a carbon nanotube (CNT) having a large specific surface area and having a shape that can be well dispersed and mixed can be obtained, it is possible to improve physical properties of the composite material including the CNT. As a result, the CNTs according to the present invention can be usefully used in various fields such as energy materials, functional composites, medicines, batteries, semiconductors, and display devices.
  • CNT carbon nanotube

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Abstract

La présente invention concerne un catalyseur sur support capable de produire des nanotubes de carbone ayant une surface spécifique élevée, et des nanotubes de carbone obtenus en utilisant le catalyseur sur support. Les nanotubes de carbone peuvent être produits à un rendement élevé selon la présente invention, et peuvent donc être efficacement utilisés dans différents domaines.
PCT/KR2014/009235 2013-09-30 2014-09-30 Catalyseur pour produire des nanotubes de carbone et nanotubes de carbone produits au moyen de celui-ci WO2015047050A1 (fr)

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EP14848695.4A EP3053878A4 (fr) 2013-09-30 2014-09-30 Catalyseur pour produire des nanotubes de carbone et nanotubes de carbone produits au moyen de celui-ci
CN201480003906.7A CN104884384B (zh) 2013-09-30 2014-09-30 用于生产碳纳米管的催化剂以及使用该催化剂生产的碳纳米管
JP2015545399A JP6131516B2 (ja) 2013-09-30 2014-09-30 カーボンナノチューブ製造用触媒及びこれを用いて製造されたカーボンナノチューブ
US14/439,168 US9956546B2 (en) 2013-09-30 2014-09-30 Catalyst for producing carbon nanotubes and carbon nanotubes produced using same

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KR10-2013-0116963 2013-09-30
KR20130116963 2013-09-30
KR20140129449A KR101508101B1 (ko) 2013-09-30 2014-09-26 높은 비표면적을 갖는 탄소나노튜브 및 그 제조 방법
KR10-2014-0129449 2014-09-26
KR10-2014-0131338 2014-09-30
KR1020140131338A KR101620720B1 (ko) 2013-09-30 2014-09-30 탄소나노튜브 제조용 촉매 및 이를 이용하여 제조된 탄소나노튜브

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110203920A (zh) * 2019-05-31 2019-09-06 西安航空职业技术学院 一种化学气相沉积改性石墨的制备方法
CN115666782A (zh) * 2020-05-29 2023-01-31 纳诺塞尔股份有限公司 用于mwcnt生产的改进催化剂

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JP2006111458A (ja) * 2004-10-12 2006-04-27 Univ Nagoya ２層カーボンナノチューブの製造方法および２層カーボンナノチューブ含有組成物
JP2008525168A (ja) * 2004-12-23 2008-07-17 ナノシル エス．エー． カーボンナノチューブの製造のための担持触媒を合成するための方法
JP2009029695A (ja) * 2007-06-29 2009-02-12 Toray Ind Inc カーボンナノチューブ集合体、分散体および導電性フィルム
JP2009508667A (ja) * 2005-09-20 2009-03-05 ナノシル エス．エー． 多層カーボンナノチューブ製造工程のための触媒系

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JP2008525168A (ja) * 2004-12-23 2008-07-17 ナノシル エス．エー． カーボンナノチューブの製造のための担持触媒を合成するための方法
JP2009508667A (ja) * 2005-09-20 2009-03-05 ナノシル エス．エー． 多層カーボンナノチューブ製造工程のための触媒系
JP2009029695A (ja) * 2007-06-29 2009-02-12 Toray Ind Inc カーボンナノチューブ集合体、分散体および導電性フィルム

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CN110203920A (zh) * 2019-05-31 2019-09-06 西安航空职业技术学院 一种化学气相沉积改性石墨的制备方法
CN115666782A (zh) * 2020-05-29 2023-01-31 纳诺塞尔股份有限公司 用于mwcnt生产的改进催化剂
CN115666782B (zh) * 2020-05-29 2024-04-19 纳诺塞尔股份有限公司 用于mwcnt生产的改进催化剂

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