WO2015047048A1 - Procédé pour contrôler la masse volumique apparente d'agglomérat de nanotubes de carbone - Google Patents

Procédé pour contrôler la masse volumique apparente d'agglomérat de nanotubes de carbone Download PDF

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WO2015047048A1
WO2015047048A1 PCT/KR2014/009231 KR2014009231W WO2015047048A1 WO 2015047048 A1 WO2015047048 A1 WO 2015047048A1 KR 2014009231 W KR2014009231 W KR 2014009231W WO 2015047048 A1 WO2015047048 A1 WO 2015047048A1
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bulk density
carbon nanotube
catalyst
nanotube aggregate
firing temperature
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PCT/KR2014/009231
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English (en)
Korean (ko)
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김성진
손승용
조동현
강경연
차진명
우지희
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주식회사 엘지화학
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Priority claimed from KR1020140129411A external-priority patent/KR101620194B1/ko
Priority claimed from KR20140129449A external-priority patent/KR101508101B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201480004965.6A priority Critical patent/CN104918881B/zh
Priority to EP14849633.4A priority patent/EP3053880B1/fr
Priority to JP2015545398A priority patent/JP6083624B2/ja
Priority to US14/438,816 priority patent/US9809458B2/en
Publication of WO2015047048A1 publication Critical patent/WO2015047048A1/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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • B01J21/18—Carbon
    • B01J21/185—Carbon nanotubes
    • 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
    • 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
    • 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
    • B01J35/31—
    • 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
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • 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
    • 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
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8877—Vanadium, tantalum, niobium or polonium

Definitions

  • the present invention relates to a method for producing a carbon nanotube aggregate, in particular a method for producing a bundle-type carbon nanotube aggregate having a bulk density controlled.
  • 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 are materials in which carbon atoms arranged in a hexagonal shape are formed in a tube shape and have a diameter of about 1 to 100 nm.
  • Such carbon nanotubes exhibit non-conductor, conductor or semiconducting properties according to their unique chirality, and the carbon atoms are connected by strong covalent bonds, so that the tensile strength is about 100 times greater than steel, and flexibility and elasticity It has excellent chemical stability.
  • the carbon nanotubes include a single-walled carbon nanotube (SW carbon nanotube) composed of one layer and a diameter of about 1 nm, and composed of two layers and a diameter of about 1.4 to 3 nm.
  • SW carbon nanotube single-walled carbon nanotube
  • DW carbon nanotubes Double-walled carbon nanotubes
  • MW carbon nanotubes multi-walled carbon nanotubes
  • carbon nanotubes Due to its characteristics such as chemical stability, excellent flexibility and elasticity, carbon nanotubes are being commercialized and applied in various fields, such as aerospace, fuel cells, composites, biotechnology, medicine, electrical and electronics, and semiconductors. have. However, the primary structure of carbon nanotubes has a limit to directly control the diameter and length of the carbon nanotubes to actual specifications for industrial applications. Constraints follow.
  • the carbon nanotubes are 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 carbon nanotubes synthesized are too small.
  • the space utilization efficiency in the reactor is greatly reduced.
  • the catalyst may be a supported catalyst, a co-precipitation catalyst, etc., in which the catalytically active component mainly has an oxide form, a partially or completely reduced form, or a hydroxide form, and which can be commonly used for the production of carbon nanotubes. It is preferable to use a double supported catalyst, which, when used, has a higher bulk density of the catalyst itself than the coprecipitation catalyst, and unlike the coprecipitation catalyst, there is less fineness of less than 10 microns, which prevents attrition that may occur during fluidization. This is because the possibility of fine powder generation can be reduced, and the mechanical strength of the catalyst itself is also excellent, which can stabilize the reactor operation.
  • the bulk density of the produced carbon nanotubes is advantageously at a certain level.
  • the problem to be solved by the present invention is a method for producing a carbon nanotube assembly that can provide a carbon nanotube having a bundle-type structure that can be dispersed and mixed well when compounding with a high yield while adjusting the bulk density To provide.
  • Another problem to be solved by the present invention is to provide a composite material including the carbon nanotube aggregate produced by the above method.
  • the present invention to solve the above problems,
  • the aluminum hydroxide is calcined at a first firing temperature of 100 ° C. or higher and 500 ° C. or lower to form a support.
  • It provides a method for producing a carbon nanotube aggregate having a bulk density of 10 kg / m 3 or more by adjusting the first firing temperature, the second firing temperature, the catalyst loading amount or the reaction time.
  • the present invention provides a carbon nanotube aggregate produced by the above method.
  • the present invention also provides a composite material comprising the carbon nanotube aggregate produced by the above method.
  • the method according to the present invention can adjust the bulk density of the carbon nanotube aggregate having a bundle form that can be well dispersed and mixed, it is possible to improve the physical properties of the composite material containing the carbon nanotubes.
  • the carbon nanotube aggregate produced by the method according to the present invention can be usefully used in various fields such as energy materials, functional composites, medicines, batteries, semiconductors, display devices, and manufacturing methods thereof.
  • 1 and 2 are graphs showing the relationship between the catalyst metal content and the bulk density value of the carbon nanotube aggregate prepared according to the embodiment of the present invention.
  • 3 and 4 are graphs showing the relationship between the bulk density value according to the number of moles of the catalyst metal to 1 mole of the organic acid of the carbon nanotube aggregate prepared according to the embodiment of the present invention.
  • FIG. 5 is an SEM image of the CNT aggregate obtained in Example 1.
  • Figure 6 is a graph showing the bulk density change of the CNT aggregate with the firing temperature in Example 2.
  • FIG 11 is a graph showing a bulk density change according to the catalyst metal content compared to the organic acid in Example 5
  • Figure 12 is an SEM image of the bundle-type carbon nanotube aggregate obtained in Example 5.
  • FIG. 13 is a graph showing the results of measuring surface resistance of polymer compounds containing carbon nanotube aggregates obtained in Example 6.
  • a supported catalyst obtained by firing aluminum hydroxide at a first firing temperature of 100 to 500 ° C. to form a support, carrying a catalyst metal precursor on the support, and then firing at a second firing temperature of 100 to 800 ° C.
  • a method for producing a carbon nanotube aggregate by contact reaction with a carbon-containing compound under heating the bulk density of 10 kg / m 3 or more by adjusting the first firing temperature, the second firing temperature, the catalyst loading amount, or the reaction time
  • a method for producing a carbon nanotube aggregate having is provided.
  • the bulk density of the carbon nanotube aggregate may be 100kg / m 3 or less.
  • At least a portion of the carbon nanotube aggregate may be bundled.
  • the second firing temperature may be 200 to 400 °C higher than the first firing temperature.
  • the first firing temperature is 300 to 500 °C
  • the second firing temperature may be that of 550 to 800 °C.
  • the catalyst metal may be one containing Fe, Co, Mo, V or a combination of two or more thereof.
  • the bulk density of the carbon nanotube aggregate increases as the second firing temperature is increased in the section of the second firing temperature is lower than 675 °C, the second firing in the section of the second firing temperature is higher than 675 °C As the temperature increases, the bulk density of the carbon nanotube aggregate may decrease.
  • the content of the catalyst metal may be 5 to 30% by weight based on the total weight of the catalyst.
  • the content of the catalyst metal (x 1 ) and the bulk density (y) of the carbon nanotube aggregate may satisfy the relationship of the following equation (1):
  • y is the bulk density (kg / m 3 )
  • x 1 is the catalyst metal content based on the total weight of the catalyst 10 to 30 (wt%)
  • a 1 is a constant of 4 to 6.5 determined by the reaction time
  • b 1 is a constant of -15 to -40 determined by the reaction time.
  • the bulk density of the carbon nanotube aggregate may be increased 1.2 to 1.5 times in proportion to the reaction time (hr) with the carbon-containing compound.
  • the preparation of the supported catalyst may include adding an organic acid to a catalyst metal in a molar ratio of 5: 1 to 30: 1, and adjusting the amount of organic acid to control the bulk density of the carbon nanotube aggregate.
  • the number of moles of catalyst metal (x 1 ) and the bulk density (y) of the carbon nanotube aggregate with respect to 1 mole of the organic acid may satisfy the relationship of Equation 2 below:
  • y is the bulk density (kg / m 3 )
  • x 2 is the number of moles of catalyst metal relative to 1 mole of the organic acid
  • a 2 is a constant of 1 to 1.5
  • b 2 is a constant of 20 to 40.
  • the reaction with the carbon-containing compound may be carried out in a fluidized bed reactor.
  • the present invention also provides a carbon nanotube aggregate produced by the method described above.
  • the present invention also provides a composite material comprising the carbon nanotube aggregate.
  • the composite material may have a conductivity satisfying the following relationship:
  • x 3 represents the bulk density of the carbon nanotube aggregate (kg / m 3 ), and R represents the surface resistance value (ohm / sq) of the composite material.
  • the present invention relates to a method that can control the bulk density in preparing a carbon nanotube aggregate.
  • the method according to the present invention is obtained by calcining aluminum hydroxide at a first firing temperature of 100 to 500 ° C. to form a support, carrying a catalyst metal precursor on the support, and then firing at a second firing temperature of 100 to 800 ° C.
  • the method for producing a carbon nanotube aggregate by a catalytic reaction of the supported catalyst with a carbon-containing compound under heating the bulk density of 10kg / m 3 or more by adjusting the first firing temperature, the second firing temperature, the catalyst loading amount or the reaction time It provides a method for producing a carbon nanotube aggregate having.
  • the bulk density of the carbon nanotube aggregates is changed by adjusting the first firing temperature, which is the support firing temperature, the second firing temperature, which is the catalyst firing temperature, the catalyst loading amount, and the reaction time.
  • the bulk density can be adjusted while preparing a bundle-type carbon nanotube aggregate, which is particularly advantageous in the dispersion of polymer composite materials.
  • the support precursor used to prepare the supported catalyst is a metal It supports a catalyst, and as the support precursor, an aluminum-based support precursor, for example, aluminum hydroxide (aluminum-tri-hydroxide, ATH) can be used.
  • the support precursor may be subjected to a pretreatment process, for example, drying at about 50 ° C. to about 150 ° C. for about 1 hour to about 24 hours.
  • the support precursor is first calcined to form a support.
  • the first firing temperature may be, for example, a range of 500 ° C. or lower, much lower than 800 ° C., which is known to convert aluminum hydroxide to alumina. That is, the support formed by the above process, for example, an aluminum-based support, preferably contains 30 wt% or more of AlO (OH) converted from Al (OH) 3 and does not include Al 2 O 3 . More specifically, the first firing process may include a heat treatment process performed at about 100 to 500 ° C, or at about 300 ° C to about 500 ° C.
  • the aluminum-based support when using an aluminum-based support as a support, may further include one or more selected from the group consisting of metal oxides, for example ZrO 2 , MgO and SiO 2 .
  • the aluminum-based support may have various shapes such as spherical or potato shape, and may have a porous structure, a molecular sieve structure, a honeycomb structure, and another suitable structure to have a relatively high surface area per unit mass or unit volume. There is no particular limitation on the same form.
  • the support precursor may have a particle diameter of about 20 to about 200 ⁇ m, porosity of about 0.1 to about 1.0 cm 3 / g, specific surface area less than about 1 m 2 / g.
  • the first firing process of forming the support from the support precursor may be performed for about 0.5 hours to about 10 hours, for example, about 1 hour to about 5 hours, but is not limited thereto.
  • the graphitized metal catalyst supported on the support serves to help the carbon components present in the gaseous carbon source combine with each other to form a hexagonal ring structure.
  • Such a graphitized metal catalyst may be used alone or as a main catalyst-catalyst complex catalyst.
  • the main catalyst may include iron (Fe) or cobalt (Co), and as the cocatalyst, one or more of molybdenum (Mo) and vanadium (V) may be used, and the content thereof is about 10 moles of the main catalyst. From 0.1 mole to about 10 moles, or from about 0.5 mole to about 5 moles.
  • the complex catalyst include at least one of FeCo, CoMo, CoV, FeCoMo, FeMoV, FeV and FeCoMoV.
  • 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, 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 , 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 paste obtained by mixing the support solution obtained through the first firing process for example, a granular aluminum support with a precursor aqueous solution of a graphitization catalyst, is dried, and after drying the paste, a second firing temperature, for example, The second firing may be performed at about 100 ° C. to about 800 ° C. to obtain a supported catalyst obtained by impregnating and coating the graphite catalyst component on the surface and pores of the support.
  • the drying may be carried out by rotary evaporation of the mixture of the precursor aqueous solution and the support of the graphitization catalyst in a vacuum of about 40 to about 100 °C within a range of about 30 minutes to about 12 hours.
  • the method may comprise the step of aging the mixture by rotation or stirring at about 45 to about 80 °C before 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 bulk density of the carbon nanotube aggregate increases as the second firing temperature increases, and in a section in which the second firing temperature is higher than 675 ° C. It can be seen that the bulk density of the carbon nanotube aggregate decreases as the second firing temperature increases. It is also possible to control the bulk density using this feature.
  • the particulate matter obtained by vacuum drying the paste in the process 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. It may be spherical or potato.
  • 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 may include, for example, about 5 to about 30% by weight of the graphite catalyst based on the total weight of the supported catalyst, but is not limited thereto.
  • the bulk density of the resulting carbon nanotube aggregate increases as the supported amount of the graphitization catalyst increases.
  • the content (x 1 ) of the catalyst metal and the bulk density (y) of the carbon nanotube aggregate may satisfy the relationship of Equation 1 below:
  • y is the bulk density (kg / m 3 )
  • x 1 is the catalyst metal content based on the total weight of the catalyst 10 to 30 (wt%)
  • a 1 is a constant of 4 to 7 determined by the reaction time
  • b 1 is a constant of -15 to -40 determined by the reaction time.
  • 1 and 2 is a graph showing the bulk density according to the catalyst metal content for the carbon nanotube aggregate prepared according to an embodiment of the present invention. 1 is the same as the other conditions but the reaction time was 1 hour, Figure 2 is the case of 2 hours. As can be seen in the figure, since the catalyst metal content of the bulk density satisfies the linear proportional relationship, it is easy to control the bulk density of the resulting carbon nanotube aggregate.
  • the bulk density of the carbon nanotube aggregates also tends to increase. According to the experiments of the present inventors, the bulk density increases by 1.2 to 1.5 times as the reaction time increases by 1 hour.
  • 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.
  • the organic acid when preparing a supported catalyst, it is possible to add the organic acid to the catalyst metal in a molar ratio of 5: 1 to 30: 1, it is also possible to control the bulk density of the carbon nanotube aggregate by adjusting the amount of the organic acid added.
  • the number of moles of catalyst metal (x 2 ) and the bulk density (y) of the carbon nanotube aggregates with respect to one mole of the organic acid may satisfy the relationship of Equation 2 below.
  • y is the bulk density (kg / m 3 )
  • x 2 is the number of moles of catalyst metal relative to 1 mole of the organic acid
  • a 2 is a constant of 1 to 1.5
  • b 2 is a constant of 20 to 40.
  • FIG. 3 and 4 are graphs showing the relationship between the bulk density according to the number of moles of the catalyst metal compared to 1 mole of the organic acid for the carbon nanotube assembly prepared in the embodiment of the present invention.
  • Figure 3 is the same condition but the reaction for 1 hour
  • Figure 4 is the result of the reaction for 2 hours.
  • the bulk density of the resulting carbon nanotube aggregates increases linearly as the number of moles of the catalyst metal increases relative to the organic acid. Using this feature, the bulk density of the result can be easily adjusted.
  • the graphitized catalyst-containing supported catalyst obtained according to the above process is contacted with a gaseous carbon source under heating conditions to form a carbon nanotube aggregate.
  • the carbon nanotube growth process will be described in more detail.
  • the carbonaceous material which is a gaseous carbon source
  • the carbonaceous material is thermally decomposed on the graphite catalyst surface.
  • Carbon nanotubes generated from the decomposed carbon-containing gas are infiltrated into the graphite catalyst and dissolved therein, and the carbon nanotubes when the penetration content exceeds the solubility limit, which is an inherent characteristic of the graphite catalyst, The nucleation of the furnace occurs to grow into carbon nanotubes.
  • the carbon nanotubes grown using the supported catalyst may have a bundle structure.
  • Such bundle-type carbon nanotubes correspond to a structure that can be dispersed and mixed well when compounding with a polymer.
  • 'bundle type' used in the present invention refers to a bundle or rope type secondary shape in which a plurality of carbon nanotubes are arranged or intertwined side by side, unless otherwise stated. do.
  • 'Non-bundle or entangled type' means a shape without a certain shape, such as a bundle or a rope shape.
  • Carbon nanotube aggregate according to the present invention obtained using the supported catalyst as described above has a bulk density of 10kg / m 3 or more, or 20 to 100 kg / m 3 , or 20 to 90 kg / m 3 , or 20 to 80 kg It may have a range of / m 3 .
  • the supported catalyst may be prepared by second firing at a temperature of 100 ° C. to 800 ° C., and the supported catalyst may be contacted with a gaseous carbon source to produce bundled carbon nanotubes.
  • Carbon nanotubes may be prepared by growing carbon nanotubes by chemical vapor phase synthesis through decomposition of a carbon source using the supported catalyst as described above.
  • the carbon nanotubes are grown on the supported catalyst by supplying a gaseous carbon source under the conditions of atmospheric pressure and high temperature Carbon nanotube aggregates can be prepared.
  • the growth of carbon nanotubes is carried out by the process of infiltrating and saturating the pyrolyzed hydrocarbons by applying high temperature heat to the graphitization catalyst as described above, and depositing carbons from the saturated graphitization catalyst to form a hexagonal ring structure. Can be.
  • the chemical vapor phase synthesis method comprises adding the supported catalyst to a horizontal fixed bed reactor or a fluidized bed reactor, the thermal decomposition temperature of the gaseous carbon source up to the melting point of the graphitization catalyst, for example from about 500 °C to about 900
  • At least one carbon source selected from saturated or unsaturated hydrocarbons having 1 to 6 carbon atoms at a temperature of about 600 ° C. to about 750 ° C., or about 660 ° C. to about 690 ° C., or the carbon source and a reducing gas (eg, It may be carried out by injecting a mixed gas of hydrogen) and a carrier gas (for example, nitrogen). Injecting a carbon source into the supported catalyst to grow the carbon nanotubes may be performed for 30 minutes to 8 hours. More preferably, a fluidized bed reactor can be used.
  • 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 a carbon source, prevents carbon nanotubes from burning at high temperatures, and helps to decompose 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 may be suitably used in the range of about 100 sccm or more and about 10,000 sccm or less.
  • the carbon nanotubes are grown by a high temperature heat treatment process as described above, the carbon nanotubes are subjected to a cooling process.
  • the carbon nanotubes 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 BET specific surface area of about 150 m 2 / g or more, preferably about 200 m 2 / g to about 500 m 2 / g can be obtained a bundle type carbon nanotubes.
  • the specific surface area can be measured by a conventional BET method.
  • the production method is able to obtain a carbon nanotube aggregate in a high yield, for example, it is possible to achieve a yield of about 5 times to 50 times, or about 10 times to 40 times.
  • the yield can be obtained by synthesizing the synthesized carbon nanotube aggregate at room temperature 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.
  • Yield (times) of carbon nanotube aggregate (total weight g after reaction-weight g of supported catalyst used) / weight of supported catalyst used g
  • the carbon nanotube aggregate may be a bundle having a flatness of about 0.9 to about 1, and as the BET specific surface area increases, each strand diameter of the carbon nanotubes is about 2 nm to about 20 nm, preferably about 3 nm to about 8 nm low diameter.
  • the flatness may be defined by the following equation.
  • the carbon nanotube aggregate has a large BET specific surface area, that is, a low diameter, and has a bundle shape, so that it is well dispersed and mixed in another material, for example, a polymer, thereby improving physical properties when forming a composite material. Will be.
  • the composite material including the carbon nanotube aggregate according to the present invention may have a conductivity that decreases as the bulk density of the carbon nanotube aggregate increases.
  • the log density (Log R) of the bulk density (kg / m 3 ) of the carbon nanotubes and the surface resistance (ohm / sq) of the composite material may satisfy the following relationship.
  • x 3 represents the bulk density (kg / m 3 ) of the CNT aggregate
  • R represents the surface resistance (ohm / sq) of the 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.
  • Fe metal catalyst was prepared as a graphitization catalyst. 2,424 g of Fe (NO 3 ) 2 .6H 2 O was added to 2,000 g of water as a precursor material of Fe. The prepared aqueous metal solution was observed as a clear solution without precipitation.
  • Flask A solution was added to Flask B such that 2,000 g of the support obtained by the first firing at 300 to 500 ° C. for 4 hours was converted to 30 moles of Fe in terms of 100 moles.
  • the graphitized catalyst metal precursor was aged by stirring in a 60 ° C. thermostat for 5 minutes to sufficiently support the ATH400. This was rotated at 80 rpm while maintaining the temperature, and dried after vacuum drying to measure the weight after drying to determine the water removal amount (about 14.1%).
  • the supported catalyst was prepared by second baking at 550 to 700 ° C. for 4 hours.
  • Carbon nanotube synthesis was carried out in a laboratory-scale fixed bed reactor using the prepared carbon nanotube supported catalyst prepared above.
  • the supported catalyst for synthesizing carbon nanotubes prepared in C was mounted at the center of a quartz tube having an inner diameter of 55 mm, and then heated up to 670 ° C. in a nitrogen atmosphere, and maintained therein, nitrogen, hydrogen, and ethylene gas.
  • the volume mixing ratio of was synthesized for 1 hour while flowing 180ml per minute in the same ratio to synthesize a predetermined amount of carbon nanotube aggregate.
  • FIG. 5 is an SEM image of the carbon nanotube aggregate.
  • a carbon nanotube aggregate was synthesized using the same catalyst as in Example 2 except that the first firing temperature was 400 ° C. and the second firing temperature was 675 ° C.
  • the reaction time is 1 hour and 2 hours
  • the yield and bulk density of the carbon nanotube aggregate according to the cobalt content change are as follows.
  • FIG. 7 is a graph showing the results of Table 3
  • FIG. 8 is SEM images of the prepared carbon nanotube aggregates.
  • a carbon nanotube aggregate was synthesized using the catalyst prepared in the same manner as in Example 3, except that Co content was set to 5.8 moles relative to 1 mole of citric acid.
  • the reaction time is 1 hour and 2 hours, the yield and bulk density of the carbon nanotube aggregate according to the cobalt content change are as follows.
  • FIG. 9 is a graph showing the results of Table 4, and FIG. 10 is an SEM image of the bulk density 81 of the prepared carbon nanotube aggregates.
  • y is the bulk density (kg / m 3 )
  • x 1 is the catalyst metal content based on the total weight of the catalyst 10 to 30 (wt%)
  • a 1 is a constant of 4 to 7 determined by the reaction time
  • b 1 is a constant of -15 to -40 determined by the reaction time.
  • FIG. 12 is an SEM image of the aggregates with bulk densities 51 and 73. From the above results, as the cobalt content was increased compared to the organic acid, the bulk density was increased, and it was confirmed that the bundle was well formed.
  • the bulk density according to the cobalt content compared to the organic acid satisfies the relationship of FIGS. 3 and 4. 3 is a result of a 1 hour reaction, and FIG. 4 is a result of a 2 hour reaction.
  • y is the bulk density (kg / m 3 )
  • x 2 is the number of moles of catalyst metal relative to 1 mole of the organic acid
  • a 2 is a constant of 1 to 1.5
  • b 2 is a constant of 20 to 40.
  • CNT aggregates were prepared by using a catalyst and reacting with a nitrogen: ethylene: hydrogen ratio of 5.5: 1: 1 for 2 hours on a laboratory scale fluidized bed reactor.
  • the catalyst for synthesizing CNTs was maintained in a quartz tube reactor having an internal diameter of 58 mm and a length of 1200 mm, heated up to 675 ° C. in a nitrogen atmosphere, and maintained a volume mixing ratio of nitrogen, hydrogen, and ethylene gas at 5.5: 1: 1.
  • a total amount of CNT aggregates were synthesized by synthesizing for 2 hours with a flow of 4000 ml per minute.
  • the yield and bulk density of the CNT aggregates are also shown.
  • x 3 represents the bulk density of the carbon nanotube aggregate (kg / m 3 ), and R represents the surface resistance value (ohm / sq) of the composite material.
  • carbon nanotube aggregates having a certain level of bulk density can be manufactured by changing process conditions such as catalyst content, reaction time, firing temperature, and the like.
  • process conditions such as catalyst content, reaction time, firing temperature, and the like.
  • bulk density it is possible to control physical properties such as conductivity of the carbon nanotube composite.
  • the method according to the present invention can adjust the bulk density of the carbon nanotube aggregate having a bundle form that can be well dispersed and mixed, it is possible to improve the physical properties of the composite material containing the carbon nanotubes.
  • the carbon nanotube aggregate produced by the method according to the present invention can be usefully used in various fields such as energy materials, functional composites, medicines, batteries, semiconductors, display devices, and manufacturing methods thereof.

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Abstract

La présente invention concerne un procédé permettant de contrôler la masse volumique apparente dans la production d'agglomérats de nanotubes de carbone. La masse volumique apparente d'agglomérats de nanotubes de carbone de type faisceau peut être aisément contrôlée selon la présente invention, et peut donc être efficacement utilisée dans différents domaines.
PCT/KR2014/009231 2013-09-30 2014-09-30 Procédé pour contrôler la masse volumique apparente d'agglomérat de nanotubes de carbone WO2015047048A1 (fr)

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CN201480004965.6A CN104918881B (zh) 2013-09-30 2014-09-30 控制碳纳米管聚集体的堆积密度的方法
EP14849633.4A EP3053880B1 (fr) 2013-09-30 2014-09-30 Procédé pour contrôler la masse volumique apparente d'agglomérat de nanotubes de carbone
JP2015545398A JP6083624B2 (ja) 2013-09-30 2014-09-30 炭素ナノチューブ集合体のバルク密度の調節方法
US14/438,816 US9809458B2 (en) 2013-09-30 2014-09-30 Method for controlling bulk density of carbon nanotube agglomerate

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KR1020140129411A KR101620194B1 (ko) 2013-09-30 2014-09-26 탄소나노튜브 집합체의 벌크 밀도 조절 방법
KR10-2014-0129449 2014-09-26
KR20140129449A KR101508101B1 (ko) 2013-09-30 2014-09-26 높은 비표면적을 갖는 탄소나노튜브 및 그 제조 방법
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