WO2016171386A1 - 고직경 저밀도 카본나노튜브 및 그 제조방법 - Google Patents
고직경 저밀도 카본나노튜브 및 그 제조방법 Download PDFInfo
- Publication number
- WO2016171386A1 WO2016171386A1 PCT/KR2016/001894 KR2016001894W WO2016171386A1 WO 2016171386 A1 WO2016171386 A1 WO 2016171386A1 KR 2016001894 W KR2016001894 W KR 2016001894W WO 2016171386 A1 WO2016171386 A1 WO 2016171386A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- carbon nanotube
- carbon
- supported
- spherical
- Prior art date
Links
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 71
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 100
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 claims description 28
- 238000010304 firing Methods 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 239000004480 active ingredient Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 239000012018 catalyst precursor Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 5
- 235000002595 Solanum tuberosum Nutrition 0.000 claims description 4
- 244000061456 Solanum tuberosum Species 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 230000006866 deterioration Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 31
- 239000002245 particle Substances 0.000 description 20
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000002194 synthesizing effect Effects 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 229910003481 amorphous carbon Inorganic materials 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000001241 arc-discharge method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- -1 2 · 6H 2 O Chemical class 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910017061 Fe Co Inorganic materials 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- JXBAVRIYDKLCOE-UHFFFAOYSA-N [C].[P] Chemical compound [C].[P] JXBAVRIYDKLCOE-UHFFFAOYSA-N 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004033 diameter control Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- 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
- B01J21/04—Alumina
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
-
- 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
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
- B01J6/001—Calcining
- B01J6/004—Calcining using hot gas streams in which the material is moved
-
- 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/84—Metals of the iron group
- B01J2523/842—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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/84—Metals of the iron group
- B01J2523/845—Cobalt
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/84—Metals of the iron group
- B01J2523/847—Nickel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/32—Specific surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/34—Length
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Definitions
- the present invention relates to a carbon nanotube having a low specific surface area and a bulk density, which is advantageous for dispersion and a method of manufacturing the same.
- carbon nanotubes are cylindrical carbon tubes having a diameter of about 3 to 150 nm, specifically about 3 to 100 nm, and having a length several times the diameter, for example, 100 times or more. Refers to. These CNTs consist of layers of aligned carbon atoms and have different types of cores. Such CNTs are also called carbon fibrils or hollow carbon fibers, for example.
- CNTs are industrially important in the production of composites due to their size and specific properties, and have high utility in the field of electronic materials, energy materials and many other fields.
- the CNT can be generally manufactured by an arc discharge method, a laser evaporation method, a chemical vapor deposition method, or the like.
- the arc discharge method and the laser evaporation method is difficult to mass-produce, there is a problem that the economical efficiency is lowered due to excessive arc production cost or laser equipment purchase cost.
- the catalyst used in the chemical vapor deposition method may be a carbon nanotube catalyst, a co-precipitation catalyst, etc., in which the catalytically active component has an oxide form, a partially or completely reduced form, or a hydroxide form, and can be generally used for preparing CNTs.
- the carbon nanotube catalyst is used, the bulk density of the catalyst itself is higher than that of the coprecipitation catalyst, and unlike the coprecipitation catalyst, the fine powder of 10 microns or less is less likely to occur in the fluidization process. This is because the possibility of fine powder generation due to attrition can be reduced, and the mechanical strength of the catalyst itself is also excellent, which can stabilize the reactor operation.
- the prepared catalyst has a problem in that diameter control is difficult in synthesizing CNTs.
- a method of controlling the diameter of CNTs by increasing the reaction temperature of a chemical vapor deposition process is mainly used. As the materials increase, there is a problem in that a separate high temperature heat treatment process for crystallizing them is additionally required.
- the problem to be solved by the present invention is to provide a high diameter low density CNT having good dispersibility.
- Another object of the present invention is to provide a method for producing the CNT by controlling the diameter while suppressing the generation of amorphous carbon during CNT synthesis.
- the present invention to solve the above problems,
- a supported catalyst on which a catalyst component and an active component are supported on a spherical ⁇ -alumina support, having a BET specific surface area of 40 m 2 / g to 120 m 2 / g and a bulk density of 60 kg / m 3 or less.
- Phosphorus carbon nanotubes are provided.
- the carbon nanotubes may have an entangled secondary structure of a potato or spherical shape.
- the present invention also to solve another technical problem,
- a catalyst component and an active component are supported on a spherical ⁇ -alumina support, and a supported catalyst calcined at 600 ° C. or lower is introduced into the reactor, and a carbon source or the carbon source is introduced into the reactor at a temperature of 650 ° C. or higher and less than 800 ° C. Injecting hydrogen gas, nitrogen gas or a mixture thereof; And
- It provides a carbon nanotube manufacturing method comprising the step of growing carbon nanotubes by decomposition of the carbon source injected on the catalyst surface.
- 6 to 10 show medium magnification (1,000-fold) SEM images of CNTs obtained using the supported catalysts obtained in Comparative Examples 1 to 3 and Examples 1 to 2, respectively.
- 11 and 12 show low magnification (35-fold) SEM images of CNTs obtained using the supported catalysts obtained in Comparative Examples 1 and 2, respectively.
- Fig. 13 shows SEM images (100,000 times) of the CNTs obtained in Examples 1-1 to 1-4.
- Fig. 14 shows SEM images (100,000 times) of CNTs obtained in Comparative Examples 4-1 to 4-4.
- the catalyst component and the active ingredient are supported on the spherical ⁇ -alumina support, and the supported catalyst calcined at 600 ° C. or lower is introduced into the reactor, and the reaction temperature is 650 ° C. or higher and 800 ° C. Injecting a carbon source or the carbon source and hydrogen gas, nitrogen gas, or a mixture thereof into the reactor at a temperature below; And
- the present invention uses an ⁇ -alumina support, but by controlling the catalyst firing temperature and the reaction temperature, the BET specific surface area is low from 40 m 2 / g to 120 m 2 / g, the bulk density is less than 60 kg / m 3 High diameter low density CNTs excellent in dispersibility can be produced.
- the supported catalyst for synthesizing CNTs is characterized in that the catalyst component and the active component are supported on a spherical ⁇ -alumina support and calcined at 600 ° C. or lower.
- alumina having a chemical formula of Al 2 O 3 is present in several different phases, for example ⁇ -, ⁇ -, ⁇ -, ⁇ -, ⁇ - and ⁇ -alumina.
- ⁇ -alumina corundum
- the oxide ions form a hexagonally packed structure and the alumina ions are symmetrically distributed in the octahedral gap.
- ⁇ -alumina has a "defective" spinel structure (the cation free spinel structure).
- the support of the catalyst may comprise ⁇ -alumina.
- ⁇ -alumina has high utility as a catalyst support due to its high porosity
- ⁇ -alumina is known to have a very low utility as a catalyst support due to its very low porosity.
- the diameter is controlled by reducing the specific surface area while suppressing the generation of amorphous carbon during CNT synthesis by controlling the firing temperature at which the supported catalyst is formed. It becomes possible.
- the supported catalyst for synthesizing CNTs according to the present invention is characterized in that the catalyst component and the active ingredient are supported on a spherical ⁇ -alumina support, and are calcined at a temperature of 600 ° C. or lower.
- the range of 400 degreeC or more and 600 degrees C or less is mentioned.
- the supported catalyst calcined in this temperature range can reduce the specific surface area and increase the diameter while minimizing the generation of amorphous carbon during CNT synthesis, and also improve the dispersibility by reducing the bulk density of CNT. .
- the term "spherical" includes a case that is substantially spherical in addition to a perfect sphere, and may include a case having an elliptic cross section such as a potato shape.
- the spherical ⁇ -alumina can be prepared by methods known in the art.
- the Bayer method for producing alumina from bauxite is widely used industrially.
- spherical ⁇ -alumina can be prepared by heating ⁇ -Al 2 O 3 or any hydrogen oxide above 1000 ° C.
- the spherical ⁇ -alumina used as the support in the present invention may be of any suitable dimension.
- the spherical ⁇ -alumina used in the present invention may have a surface area of, for example, about 1 m 2 / g to about 50 m 2 / g as measured by the BET method.
- the spherical ⁇ -alumina used as the support has a very low porosity due to its smooth surface unlike the conventional support, and may have a pore volume of 0.001 to 0.1 cm 3 / g, for example.
- the spherical ⁇ -alumina which is a support, may be loaded with a relatively low content of metal, for example, about 10 to 25 parts by weight of the catalyst component and the active component based on 100 parts by weight of the spherical ⁇ -alumina, Or in an amount of about 15 to 20 parts by weight. Sufficient catalytic activity can be exhibited at such supported contents.
- the catalyst component and the active component supported on the spherical ⁇ -alumina can be used in a weight ratio of 10 to 30: 1 to 14, and can exhibit better CNT production activity in this content range.
- the catalyst component used in the present invention may be one or more selected from Fe, Co and Ni, for example Fe salt, Fe oxide, Fe compound, Co salt, Co oxide, Co compound, Ni salt, Ni oxide, Ni compound It may be one or more selected from the group consisting of, and as another example Fe (NO 3 ) 2 ⁇ 6H 2 O, Fe (NO 3 ) 2 ⁇ 9H 2 O, Ni (NO 3 ) 2 ⁇ 6H 2 O, Co (NO 3 ) a nitride such as 2 ⁇ 6H 2 O, or the like.
- the active ingredient used in the present invention may be at least one of Mo and V, for example, may be Mo salt, Mo oxide, Mo compound, V salt, V oxide, V compound and the like, as another example, A nitride such as (NH 4 ) 6 Mo 7 O 24 ⁇ 4H 2 O can be dissolved in distilled water and used.
- the supported catalyst for synthesizing CNTs of the present invention as described above can be prepared by the impregnation method.
- the aqueous solution is formed by mixing the Al-based support in the aqueous metal solution containing the catalyst component precursor and the active component precursor, wherein the catalyst component, active Components and spherical ⁇ -alumina supports, which have already been described above.
- the concentration of the metal aqueous solution is more efficient to use, for example, 0.1 to 0.4 g / ml, or 0.1 to 0.3 g / ml.
- the content of the spherical ⁇ -alumina support mixed with the aqueous metal solution may be, for example, about 10 to 25 parts by weight based on 100 parts by weight of the spherical ⁇ -alumina, or It can be used to be supported in an amount of about 15 to 20 parts by weight.
- step (2) of the preparation method Aging impregnation of the supported catalyst precursor solution in step (2) of the preparation method to obtain a mixture, wherein the impregnation is not limited to this, but 30 minutes in a temperature range of 20 to 100 °C, or 60 to 100 °C It can be carried out for 15 to 15 hours, or 1 to 15 hours, it is possible to provide a high supporting efficiency in this range.
- step (3) of the production method the mixture resulting from the aging impregnation obtained in step (2) is vacuum dried to coat the catalyst component and the active ingredient on the surface of the support.
- the vacuum drying is to dry by rotary evaporation under vacuum, for example, can be carried out within 1 hour, or 1 minute to 1 hour under 45 to 80 °C, drying the excess metal salt remaining without impregnation in the support.
- the process makes it possible to provide a coating impregnation of a uniform alumina surface.
- vacuum in the vacuum drying described herein is not particularly limited as long as it corresponds to the vacuum range that is typically applied to vacuum drying.
- step (4) of the production method the resultant obtained by vacuum drying of step (3) is fired to form a supported catalyst of the present invention, which is a final result, and such firing is performed in a range of about 400 to 600 ° C. It may be done in air or under an inert atmosphere. The firing time is not limited thereto, but may be performed within about 30 minutes to 5 hours.
- the vacuum drying of the step (3) before the firing of the step (4) may be carried out one or more times pre-baking at about 250 to 400 °C, in this case, the entire supported catalyst immediately before the pre-firing Up to 50% of the precursor aqueous solution is used by impregnating the amorphous ⁇ -alumina support, and the remaining amount of the supported catalyst precursor aqueous solution is impregnated into the spherical ⁇ -alumina support immediately after the preliminary firing or immediately before the firing.
- the bulk shape of the supported catalyst prepared as described above depends on the bulk shape of the spherical ⁇ -alumina support used. That is, the supported catalyst for synthesizing CNTs may have a spherical bulk shape and mainly have a structure in which a catalyst component is coated on one or multiple layers (two or three or more layers) on the surface of the support, and these may not have a continuous coating layer structure. It may be desirable to have a discontinuous coating structure in terms of CNT synthesis.
- the supported catalyst for preparing CNTs provided by the present invention may have, for example, a particle size or an average particle diameter of about 30 to about 150 ⁇ m, and a surface particle size of SEM observation in the range of about 10 to 50 nm, in which CNT diameter Preferred in terms of control and catalytic activity.
- the supported catalyst coated with the catalyst component and the active ingredient on the surface of the spherical ⁇ -alumina support is ultrasonic (ultrasonic) having a particle size of 32 ⁇ m or less based on the particle size measurement standard in consideration of the particle size or the average particle size range of the alumina support.
- the number average particle size measurement may have a range of 5% or less, specifically 3% or less.
- the fine powder is an aggregate of the catalyst material and the active material attached to the catalyst, and is not filtered out when sieved, but is different in particle size and catalyst activity from the catalyst-active material well coated on the support.
- island-like aggregates attached to the catalyst significantly lower the yield of CNTs, and because the materials are rather weakly attached to the catalyst, they are separated at the time of ultrasonication to generate fine powder.
- the ultrasonic differential amount refers to the number average particle diameter differential amount measured by the particle size analyzer after the ultrasonic treatment, wherein the support includes a multilayer support.
- the supported catalyst for synthesizing CNTs obtained by the present invention is preferably spherical in view of specific surface area, and the supported catalyst for synthesizing CNTs prepared in the present invention is also spherical, almost spherical, or substantially close to spherical. It became.
- the process for preparing CNTs from the supported catalyst obtained by the above-described method includes, but is not limited to:
- the reactor may be a fixed bed reactor or a fluidized bed reactor without limitation.
- the reaction temperature is in the range of 650 to less than 800 °C to reduce the specific surface area of the CNT produced while minimizing the generation of amorphous carbon
- the diameter of the resulting CNTs can be increased.
- the yield is lowered while maintaining the bulk size of the CNT, as a result, as the bulk density is lowered, dispersibility may be improved.
- CNTs having an entangled secondary structure and having a spherical bulk shape are manufactured at high diameter (low BET specific surface area) and low bulk density. It becomes possible.
- CNTs of the present invention obtained according to the above production method may have a particle diameter or average particle diameter of 100 to 800 ⁇ m and the strand diameter of the CNT is 10 to 50nm.
- the BET specific surface area is low, 40 m 2 / g to 120 m 2 / g, bulk density 60 kg / m 3 or less, or 20 kg / m 3 or more, 60 kg / m 3 or less, flatness 0.9
- the particle size distribution value Dcnt may be a potato or sphere entangled type (entangled type) of 0.5 to 1.0.
- 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 BELSORP-mini II manufactured by BEL Japan. .
- the term "bulk density” is defined by Equation 1 below, by adjusting the firing temperature of the supported catalyst and increasing the reaction temperature during CNT synthesis, the density distribution of CNTs grown therefrom may also have a specific range. have.
- the flatness and the bundle type can be obtained by a unique process prepared using the supported catalyst of the present invention described above.
- the flatness ratio is defined by the following Equation 2.
- Flatness shortest diameter through the center of CNT / maximum diameter through the center of CNT.
- the particle size distribution value Dcnt may be defined by Equation 3 below.
- Dn90 is the number average particle diameter measured under 90% in absorbing mode using Microtrac particle size analyzer after 3 hours of CNT in distilled water
- Dn10 is the number average particle diameter measured under 10% reference
- Dn50 is the number average particle diameter measured on a 50% basis.
- the CNT of the present invention can be used as a raw material in the electric field, the electronic field, the energy field, etc., and can also be used as the reinforcing material in the plastic field.
- Flask A was prepared completely dissolved in 15.0 ml of distilled water.
- Carbon nanotube synthesis was tested in a laboratory scale fixed bed reactor using the catalysts for synthesizing CNTs prepared in Examples 1 to 4 and Comparative Examples 1 to 4. Specifically, the catalyst for synthesizing CNT prepared in the above process was mounted in the middle of a quartz tube having an internal diameter of 55 mm, and then heated up to 650 ° C. in a nitrogen atmosphere and maintained therein, while flowing hydrogen gas at a flow rate of 60 sccm. Synthesis was carried out for 2 hours to synthesize a predetermined amount of carbon nanotube aggregates. The CNT yield, bulk density and specific surface area at this time are shown in Table 4 below.
- FIGS. 1 to 5 are high magnification (100,000 times) SEM images of CNTs obtained in Comparative Examples 1 to 3 and Examples 1 to 2, respectively, and FIGS. 6 to 10 were obtained in Comparative Examples 1 to 3 and Examples 1 to 2, respectively. It is a medium magnification (1,000 times) SEM image of CNT, and FIG. 11 and FIG. 12 show the low magnification (35 times) SEM image of CNT obtained in Comparative Example 1 and Example 2, respectively.
- Example 1 Using the supported catalysts obtained in Example 1 and Comparative Example 4, except that the reaction temperature of the reactor in which CNTs are synthesized is changed as shown in Table 5 below, and the reaction time was changed to 3 hours. CNTs were prepared by following the same process, and the CNT yield and specific surface area are shown in Table 5 below.
- Example 1-1 Example 1 800 5 25 Example 1-2 750 13 65 Example 1-3 700 12 81 Example 1-4 650 27 117 Comparative Example 4-1 Comparative Example 4 800 15 35 Comparative Example 4-2 750 73 178 Comparative Example 4-3 700 87 184 Comparative Example 4-4 650 42 218
- the diameter of CNT was hardly changed until the CVD reaction temperature of 750 ° C., but a sudden diameter change occurred at 800 ° C.
- the diameter of the CNTs differs depending on the firing temperature at which the supported catalyst is prepared. It can be seen that the diameter tends to increase gradually.
- FIG. 16 shows that even though CNTs were prepared at 700 ° C. or less, the D-peak did not broaden but crystallinity was improved.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
구분 | 지지체 (mg) | 금속 전구체 함량 (mg) | |||
Fe(NO3)2 ·9H2O | Co(NO3)2 ·6H2O | (NH4)6Mo7O24 | NH4VO3 | ||
실시예 1 ~ 4 | 12.5(구형상 α-Al2O3) | 2.391 | 7.341 | 0.552 | 0.344 |
비교예 1 ~ 3 | 12.5(구형상 α-Al2O3) | 2.391 | 7.341 | 0.552 | 0.344 |
비교예 4 | 12.5(γ-Al2O3) | 3.984 | 12.234 | 0.920 | 0.574 |
구분 | 지지체(중량부) | 금속 함량 (중량부) | 총 금속 함량 | ||||
Fe | Co | Mo | V | 중량부 | 중량% | ||
실시예 1 ~ 4 | 구형상α-Al2O3100 | 2.6 | 11.9 | 2.4 | 1.2 | 18.1 | 15.3 |
비교예 1~3 | 구형상α-Al2O3100 | 2.6 | 11.9 | 2.4 | 1.2 | 18.1 | 15.3 |
비교예 4 | γ-Al2O3100 | 4.4 | 19.8 | 4.0 | 2.0 | 30.2 | 23.2 |
구분 | 소성 분위기 | 소성온도(℃) |
비교예 1 | 공기중 | 680 |
비교예 2 | 660 | |
비교예 3 | 620 | |
실시예 1 | 600 | |
실시예 2 | 400 | |
실시예 3 | 질소 대기 | 600 |
실시예 4 | 400 | |
비교예 4 | 공기중 | 715 |
구분 | 소성온도(℃) | CNT 수율(CNT g/촉매 g) | CNT 벌크밀도(kg/m3) | CNT BET 비표면적(m2/g) |
비교예 1 | 680 | 73 | 114 | 202 |
비교예 2 | 660 | 60 | 112 | 175 |
비교예 3 | 620 | 51 | 110 | 145 |
실시예 1 | 600 | 27 | 58 | 117 |
실시예 2 | 400 | 19 | 32 | 96 |
실시예 3 | 600 | 22 | 36 | 103 |
실시예 4 | 400 | 20 | 31 | 96 |
구분 | 담지촉매 | 반응온도(℃) | CNT 수율(CNT g/촉매 g) | CNT BET 비표면적(m2/g) |
실시예 1-1 | 실시예 1 | 800 | 5 | 25 |
실시예 1-2 | 750 | 13 | 65 | |
실시예 1-3 | 700 | 12 | 81 | |
실시예 1-4 | 650 | 27 | 117 | |
비교예 4-1 | 비교예 4 | 800 | 15 | 35 |
비교예 4-2 | 750 | 73 | 178 | |
비교예 4-3 | 700 | 87 | 184 | |
비교예 4-4 | 650 | 42 | 218 |
Claims (16)
- 구형상 α-알루미나 지지체에 촉매성분 및 활성성분이 지지되어 있는 담지촉매 상에 성장되어 있으며,BET 비표면적이 40 m2/g 내지 120 m2/g 이고, 벌크밀도가 60kg/m3 이하인 것인 카본나노튜브.
- 제1항에 있어서, 포테이토 또는 구 형상의 인탱글 타입(entangled)의 2차 구조를 갖는 카본나노튜브.
- 구형상 α-알루미나 지지체에 촉매성분 및 활성성분이 지지되어 있으며, 600℃ 이하에서 소성된 담지촉매를 반응기 내부에 투입하고, 650℃ 이상 800℃ 미만의 온도에서 반응기 내부로 탄소 공급원 또는 상기 탄소공급원과 수소가스, 질소가스 또는 이들의 혼합가스를 주입하는 단계; 및상기 촉매 표면 위에서 주입된 탄소 공급원의 분해를 통해 카본나노튜브를 성장시키는 단계;를 포함하는 제1항 또는 제2항의 카본나노튜브 제조방법.
- 제3항에 있어서,상기 소성 온도가 400℃ 내지 600℃인 것인 카본나노튜브제조방법.
- 제3항에 있어서,상기 촉매성분 및 활성성분이 구형상 α-알루미나 100중량부를 기준으로 약 10 내지 25중량부의 함량으로 담지되는 것인 카본나노튜브 제조방법.
- 제3항에 있어서,상기 촉매성분 및 활성성분이10 내지 30 : 1 내지 14의 중량비를 갖는 것인 카본나노튜브 제조방법.
- 제3항에 있어서,상기 촉매성분이 Fe, Co 및 Ni로부터 선택된 1종 이상을 포함하는 것인 카본나노튜브 제조방법.
- 제3항에 있어서,상기 활성성분이 Mo 및 V 중 1종 이상을 포함하는 것인 카본나노튜브 제조방법.
- 제3항에 있어서,상기 담지 촉매가 함침법으로 제조된 것인 카본나노튜브 제조방법.
- 제3항에 있어서,상기 담지 촉매의 울트라소닉 미분량이 5% 이내인 것인 카본나노튜브 제조방법.
- 제3항에 있어서, 상기 담지촉매가촉매성분 전구체 및 활성성분 전구체를 포함하는 금속 수용액에 구형상 α-알루미나 지지체를 혼합하여 담지촉매 전구체 함유 수용액을 형성하는 단계;상기 담지촉매 전구체 함유 수용액을 숙성 함침시켜 혼합물을 수득하는 단계;상기 혼합물을 진공건조하여 상기 지지체 표면에 상기 촉매성분 및 활성성분을 코팅하는 단계; 및상기 진공건조에 의해 얻어진 결과물을 600℃ 이하의 온도에서 소성하여 담지촉매를 형성하는 단계;를 포함하는 방법에 의해 제조된 것인 카본나노튜브 제조방법.
- 제11항에 있어서,상기 금속 수용액의 농도가 0.1 내지 0.4 g/ml인 것인 카본나노튜브 제조방법.
- 제11항에 있어서,상기 숙성 함침 공정이 20℃ 내지 100℃의 온도에서 30분 내지 15시간 동안 수행되는 것인 카본나노튜브 제조방법.
- 제11항에 있어서,상기 진공 건조 공정이 45 내지 80℃ 하에 1분 내지 1시간 동안 수행되는 것인 카본나노튜브 제조방법.
- 제11항에 있어서,상기 진공 건조 후 소성 전 250℃ 내지 400℃ 하에 예비 소성을 1회 이상 수행하는 것인 카본나노튜브 제조방법.
- 제11항에 있어서,상기 반응기가 고정층 반응기 또는 유동층 반응기인 것인 카본나노튜브 제조방법.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16745602.9A EP3290391B1 (en) | 2015-04-21 | 2016-02-26 | Large-diameter, low-density carbon nanotube, and preparation method therefor |
US15/123,180 US10399855B2 (en) | 2015-04-21 | 2016-02-26 | Carbon nanotubes having larger diameter and lower bulk density and process for preparing same |
JP2016551842A JP6631847B2 (ja) | 2015-04-21 | 2016-02-26 | 高直径かつ低密度のカーボンナノチューブ及びその製造方法 |
CN201680000854.7A CN106458593B (zh) | 2015-04-21 | 2016-02-26 | 大直径、低密度碳纳米管以及制备该碳纳米管的方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020150055635A KR101735180B1 (ko) | 2015-04-21 | 2015-04-21 | 고직경 저밀도 카본나노튜브 및 그 제조방법 |
KR10-2015-0055635 | 2015-04-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016171386A1 true WO2016171386A1 (ko) | 2016-10-27 |
Family
ID=57143267
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2016/001894 WO2016171386A1 (ko) | 2015-04-21 | 2016-02-26 | 고직경 저밀도 카본나노튜브 및 그 제조방법 |
Country Status (6)
Country | Link |
---|---|
US (1) | US10399855B2 (ko) |
EP (1) | EP3290391B1 (ko) |
JP (1) | JP6631847B2 (ko) |
KR (1) | KR101735180B1 (ko) |
CN (1) | CN106458593B (ko) |
WO (1) | WO2016171386A1 (ko) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020525385A (ja) * | 2017-12-26 | 2020-08-27 | エルジー・ケム・リミテッド | エンタングル型カーボンナノチューブ及びその製造方法 |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102124951B1 (ko) | 2017-03-17 | 2020-06-22 | 주식회사 엘지화학 | 번들형 탄소나노튜브 및 이의 제조방법 |
CN107626334A (zh) * | 2017-10-19 | 2018-01-26 | 焦作集越纳米材料技术有限公司 | 一种碳纳米管催化剂的制备方法 |
CN108163829A (zh) * | 2017-11-20 | 2018-06-15 | 肇庆市华师大光电产业研究院 | 一种玻璃碳/多壁碳纳米管复合电极及其制备方法和应用 |
JP7086419B2 (ja) * | 2018-07-27 | 2022-06-20 | エルジー・ケム・リミテッド | カーボンナノチューブ、その製造方法およびこれを含む一次電池用の正極 |
KR102450747B1 (ko) | 2018-07-27 | 2022-10-06 | 주식회사 엘지화학 | 탄소나노튜브의 제조방법 |
CN113574013B (zh) * | 2019-03-07 | 2024-01-26 | 株式会社Lg新能源 | 碳纳米管以及包括所述碳纳米管的电极和二次电池 |
JP7255281B2 (ja) * | 2019-03-26 | 2023-04-11 | 日本ゼオン株式会社 | 触媒担持体の製造方法および繊維状炭素ナノ構造体の製造方法 |
JP7093085B2 (ja) * | 2020-05-12 | 2022-06-29 | 株式会社 東北テクノアーチ | 多孔質炭素材料 |
CN115254133A (zh) * | 2022-05-16 | 2022-11-01 | 湖北冠毓新材料科技有限公司 | 一种负载型高导电碳纳米管催化剂的制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20080052581A (ko) * | 2005-09-20 | 2008-06-11 | 에스.에이. 나노실 | 다중벽 탄소 나노튜브 생산 공정을 위한 촉매 시스템 |
KR20130082460A (ko) * | 2012-01-11 | 2013-07-19 | 주식회사 엘지화학 | 카본나노튜브 및 그 제조방법 |
KR20150007267A (ko) * | 2013-07-10 | 2015-01-20 | 주식회사 엘지화학 | 담지 촉매 및 이를 이용하여 제조된 탄소나노튜브 |
KR20150037601A (ko) * | 2013-09-30 | 2015-04-08 | 주식회사 엘지화학 | 탄소나노튜브 집합체의 벌크 밀도 조절 방법 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006505483A (ja) * | 2002-11-26 | 2006-02-16 | カーボン ナノテクノロジーズ インコーポレーテッド | カーボンナノチューブ微粒子、組成物及びその使用法 |
FR2881418B1 (fr) | 2005-02-03 | 2007-04-27 | Centre Nat Rech Scient | Materiaux a base de nanofibres ou nanotubes enchevetres, leur preparation et utilisations |
JP4849437B2 (ja) * | 2005-04-22 | 2012-01-11 | 国立大学法人名古屋大学 | 3層カーボンナノチューブの製造方法および3層カーボンナノチューブ含有組成物 |
FR2921391B1 (fr) | 2007-09-24 | 2010-08-13 | Arkema France | Procede de preparation de materiaux composites |
JP2011063458A (ja) | 2009-09-15 | 2011-03-31 | Otsuka Chem Co Ltd | カーボンナノチューブ粉体、電極用導電助剤及びそれを用いた電極並びに該電極を用いた蓄電デバイス |
GB201100712D0 (en) * | 2011-01-17 | 2011-03-02 | Bio Nano Consulting | Cross-linked carbon nanotube networks |
KR101424910B1 (ko) | 2012-01-11 | 2014-07-31 | 주식회사 엘지화학 | 카본나노튜브 및 그 제조방법 |
WO2013158157A1 (en) | 2012-04-16 | 2013-10-24 | Seerstone Llc | Methods and reactors for producing solid carbon nanotubes, solid carbon clusters, and forests |
KR101535388B1 (ko) * | 2013-07-19 | 2015-07-08 | 주식회사 엘지화학 | 담지촉매, 이의 제조방법 및 이를 이용하여 제조된 탄소나노구조체의 2차구조물 |
KR101785773B1 (ko) | 2015-02-06 | 2017-10-17 | 주식회사 엘지화학 | 구 형상의 알파-알루미나를 함유하는 카본나노튜브 합성용 담지촉매 및 그의 제조방법 |
-
2015
- 2015-04-21 KR KR1020150055635A patent/KR101735180B1/ko active IP Right Grant
-
2016
- 2016-02-26 EP EP16745602.9A patent/EP3290391B1/en active Active
- 2016-02-26 WO PCT/KR2016/001894 patent/WO2016171386A1/ko active Application Filing
- 2016-02-26 JP JP2016551842A patent/JP6631847B2/ja active Active
- 2016-02-26 CN CN201680000854.7A patent/CN106458593B/zh active Active
- 2016-02-26 US US15/123,180 patent/US10399855B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20080052581A (ko) * | 2005-09-20 | 2008-06-11 | 에스.에이. 나노실 | 다중벽 탄소 나노튜브 생산 공정을 위한 촉매 시스템 |
KR20130082460A (ko) * | 2012-01-11 | 2013-07-19 | 주식회사 엘지화학 | 카본나노튜브 및 그 제조방법 |
KR20150007267A (ko) * | 2013-07-10 | 2015-01-20 | 주식회사 엘지화학 | 담지 촉매 및 이를 이용하여 제조된 탄소나노튜브 |
KR20150037601A (ko) * | 2013-09-30 | 2015-04-08 | 주식회사 엘지화학 | 탄소나노튜브 집합체의 벌크 밀도 조절 방법 |
Non-Patent Citations (4)
Title |
---|
CHAI, SIANG PIAO ET AL.: "The Effect of Catalyst Calcination Temperature on the Diameter of Carbon Nanotubes synthesized by the Decomposition of Methane", CARBON, vol. 45, 2007, pages 1535 - 1541, XP022101691 * |
KIBRIA, A. K. M. FAZLE ET AL.: "Synthesis of Carbon Nanotubes over Nickel-Iron Catalysts supported on Alumina under Controlled Conditions", CATALYSIS LETTERS, vol. 71, no. 3-4, 2001, pages 229 - 236, XP008128751 * |
RUMMELI, MARK H. ET AL.: "Investigating the Outskirts of Fe and Co Catalyst Particles in Alumina-supported Catalytic CVD Carbon Nanotube Growth", ACS NANO, vol. 4, no. 2, 2010, pages 1146 - 1152, XP055040807 * |
See also references of EP3290391A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2020525385A (ja) * | 2017-12-26 | 2020-08-27 | エルジー・ケム・リミテッド | エンタングル型カーボンナノチューブ及びその製造方法 |
US11618679B2 (en) | 2017-12-26 | 2023-04-04 | Lg Chem, Ltd. | Entangled-type carbon nanotubes and method for preparing the same |
US11987499B2 (en) | 2017-12-26 | 2024-05-21 | Lg Chem, Ltd. | Entangled-type carbon nanotubes and method for preparing the same |
Also Published As
Publication number | Publication date |
---|---|
KR101735180B1 (ko) | 2017-05-12 |
US20180162734A1 (en) | 2018-06-14 |
EP3290391A1 (en) | 2018-03-07 |
CN106458593B (zh) | 2019-10-29 |
JP2018513083A (ja) | 2018-05-24 |
EP3290391B1 (en) | 2022-05-11 |
KR20160125030A (ko) | 2016-10-31 |
EP3290391A4 (en) | 2018-12-19 |
CN106458593A (zh) | 2017-02-22 |
JP6631847B2 (ja) | 2020-01-15 |
US10399855B2 (en) | 2019-09-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2016171386A1 (ko) | 고직경 저밀도 카본나노튜브 및 그 제조방법 | |
WO2016126133A1 (ko) | 고밀도 번들형 카본나노튜브 및 그의 제조방법 | |
WO2015005709A1 (ko) | 담지촉매, 탄소나노튜브 집합체 및 그 제조방법 | |
WO2015190774A1 (ko) | 벌크밀도가 조절된 탄소나노튜브 응집체의 제조방법 | |
WO2013105780A1 (ko) | 카본나노튜브용 균질 담지 촉매의 제조방법 | |
WO2016140443A1 (ko) | 수열합성 공침법을 이용하여 제조된 촉매 및 이를 이용하여 제조된 카본나노튜브 | |
WO2017039132A1 (ko) | 카본나노튜브의 정제방법 | |
KR102085940B1 (ko) | 다중벽 탄소나노튜브의 대량 생산을 위한 촉매 | |
KR20130082460A (ko) | 카본나노튜브 및 그 제조방법 | |
WO2017018667A1 (ko) | 열안정성이 개선된 카본나노튜브 | |
WO2022124799A1 (ko) | 탄소나노튜브 제조용 담지촉매 | |
KR101778834B1 (ko) | 탄소나노튜브 제조방법 및 이를 이용하여 제조된 탄소나노튜브 | |
WO2017048053A1 (ko) | 결정성이 개선된 카본나노튜브 | |
WO2016126132A1 (ko) | 부정형 알파-알루미나를 함유하는 카본나노튜브 합성용 촉매 및 이를 이용한 카본나노튜브의 제조방법 | |
WO2020060274A1 (ko) | 계층화된 제올라이트 및 이의 제조방법 | |
KR20130081916A (ko) | 카본나노튜브용 균질 담지 촉매의 제조방법 및 이에 사용되는 장치 | |
KR102379594B1 (ko) | 인탱글형 탄소나노튜브 및 이의 제조방법 | |
WO2015047050A1 (ko) | 탄소나노튜브 제조용 촉매 및 이를 이용하여 제조된 탄소나노튜브 | |
KR101484364B1 (ko) | 카본나노튜브 합성용 담지 촉매의 제조방법 | |
KR101548410B1 (ko) | 카본나노튜브용 균질 담지 촉매, 이의 제조방법, 및 이에 사용되는 제조장치 | |
WO2013066105A1 (ko) | 이중벽 탄소나노튜브 및 그 제조방법 | |
WO2018160042A1 (ko) | 다중벽 탄소나노튜브의 대량 생산을 위한 촉매 | |
WO2024091032A1 (ko) | 탄소나노튜브 제조용 촉매 및 이의 제조방법 | |
WO2024096507A1 (ko) | 메탄 개질용 촉매 및 이의 제조방법 | |
WO2023136631A1 (ko) | 번들형 탄소나노튜브 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2016551842 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15123180 Country of ref document: US |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16745602 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2016745602 Country of ref document: EP |