KR20230150529A - Supported Catalyst for Synthesizing Multi-walled Carbon Nanotube and Manufacturing Method thereof - Google Patents
Supported Catalyst for Synthesizing Multi-walled Carbon Nanotube and Manufacturing Method thereof Download PDFInfo
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- KR20230150529A KR20230150529A KR1020220050033A KR20220050033A KR20230150529A KR 20230150529 A KR20230150529 A KR 20230150529A KR 1020220050033 A KR1020220050033 A KR 1020220050033A KR 20220050033 A KR20220050033 A KR 20220050033A KR 20230150529 A KR20230150529 A KR 20230150529A
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- supported catalyst
- walled carbon
- carbon nanotube
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- 239000003054 catalyst Substances 0.000 title claims abstract description 111
- 239000002048 multi walled nanotube Substances 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 230000002194 synthesizing effect Effects 0.000 title description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000395 magnesium oxide Substances 0.000 claims description 61
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 61
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 61
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 59
- 239000002243 precursor Substances 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- 230000015572 biosynthetic process Effects 0.000 claims description 21
- 229910017052 cobalt Inorganic materials 0.000 claims description 21
- 239000010941 cobalt Substances 0.000 claims description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 21
- 238000003786 synthesis reaction Methods 0.000 claims description 20
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 19
- 229910052750 molybdenum Inorganic materials 0.000 claims description 19
- 239000011733 molybdenum Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 17
- 239000011572 manganese Substances 0.000 claims description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000002230 thermal chemical vapour deposition Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 3
- 238000003421 catalytic decomposition reaction Methods 0.000 description 20
- 239000011148 porous material Substances 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- 239000002041 carbon nanotube Substances 0.000 description 15
- 229910021393 carbon nanotube Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000010304 firing Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 238000002411 thermogravimetry Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000408529 Libra Species 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VSOYJNRFGMJBAV-UHFFFAOYSA-N N.[Mo+4] Chemical compound N.[Mo+4] VSOYJNRFGMJBAV-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- -1 iron carbides Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910001337 iron nitride Inorganic materials 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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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
- B01J37/02—Impregnation, coating or precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—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
- B01J23/74—Iron group metals
- B01J23/75—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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/02—Solids
- B01J35/10—Solids characterised by their surface properties or porosity
- B01J35/1004—Surface area
- B01J35/1014—10-100 m2/g
-
- 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
- B01J35/02—Solids
- B01J35/10—Solids characterised by their surface properties or porosity
- B01J35/1004—Surface area
- B01J35/1019—100-500 m2/g
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- B01J35/613—
-
- B01J35/615—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- 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
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- 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
- C01B2202/06—Multi-walled nanotubes
Abstract
본 발명은 다중벽 탄소나노튜브를 합성하는데 사용되는 담지촉매의 제조방법에 관한 것으로, 본 발명의 담지촉매는 금속촉매 및 상기 금속촉매를 함유하는 다공성의 담지체로 구성되며, 이를 제조하는 방법에 관한 것이다.The present invention relates to a method for manufacturing a supported catalyst used to synthesize multi-walled carbon nanotubes. The supported catalyst of the present invention is composed of a metal catalyst and a porous support containing the metal catalyst, and relates to a method for manufacturing the same. will be.
Description
본 발명은 다중벽 탄소나노튜브를 합성하는데 사용되는 담지촉매의 제조방법에 관한 것으로, 본 발명의 담지촉매는 금속촉매 및 상기 금속촉매를 함유하는 다공성의 담지체로 구성되며, 이를 제조하는 방법에 관한 것이다.The present invention relates to a method for manufacturing a supported catalyst used to synthesize multi-walled carbon nanotubes. The supported catalyst of the present invention is composed of a metal catalyst and a porous support containing the metal catalyst, and relates to a method for manufacturing the same. will be.
탄소나노튜브는 1개의 탄소 원자가 3개의 다른 탄소 원자와 결합한 육각형 벌집 모양의 흑연면이 나노크기의 직경으로 둥글게 말린 형태를 갖고 있으며, 크기나 형태에 따라 독특한 물리적 성질을 갖는 거대 분자이다. 속이 비어 있어 가볍고 전기 전도도는 구리만큼 좋으며, 열전도도는 다이아몬드만큼 우수하고 인장력은 철강에 못지 않다. 말려진 형태에 따라서 단일벽 나노튜브(single walled carbon nanotube, SWCNT), 다중벽 나노튜브(multi-walled carbon nanotube, MWCNT), 다발형 나노튜브(rope carbon nanotube)로 구분되기도 한다.Carbon nanotubes are macromolecules that have a hexagonal honeycomb-shaped graphite surface in which one carbon atom is bonded to three other carbon atoms, rolled up to a nano-sized diameter, and have unique physical properties depending on their size and shape. Because it is hollow, it is light and has electrical conductivity as good as copper, thermal conductivity as good as diamond, and tensile strength as good as steel. Depending on the rolled shape, they are classified into single-walled carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs), and rope carbon nanotubes.
이러한 탄소나노튜브는 우수한 전기적, 열적, 기계적 성질을 가지고 있으므로 다방면에 응용될 수 있는데, 예를 들어 고집적 메모리, 평판형 디스플레이용 전자 방출기, 투명 또는 반투명의 고성능 도전물질, 스캐닝 프로브 마이크로스코프의 탐침, 화학센서 등으로 응용 연구가 행해지고 있다.These carbon nanotubes have excellent electrical, thermal, and mechanical properties, so they can be applied in a variety of fields, such as highly integrated memories, electron emitters for flat-panel displays, transparent or translucent high-performance conductive materials, probes for scanning probe microscopes, etc. Applied research is being conducted on chemical sensors, etc.
탄소나노튜브는 일반적으로 전기방전법, 레이저 증착법, 플라즈마 화학기상증착법, 열화학증착법, 기상합성법 및 전기분해법 등의 방법으로 제조될 수 있으며, 이중 기상합성법의 경우 기판을 사용하지 않고 반응로 안에 탄소를 함유하고 있는 가스와 촉매금속을 직접 공급하여 반응시켜 탄소나노튜브의 증착물을 형성하기 때문에 고순도의 탄소나노튜브를 대량으로 합성할 수 있으면서도 경제성이 뛰어나 가장 각광받고 있다.Carbon nanotubes can generally be manufactured by methods such as electric discharge, laser deposition, plasma chemical vapor deposition, thermochemical vapor deposition, vapor phase synthesis, and electrolysis. In the case of the vapor phase synthesis method, carbon is stored in a reactor without using a substrate. Since the contained gas and catalyst metal are directly supplied and reacted to form a carbon nanotube deposit, high-purity carbon nanotubes can be synthesized in large quantities and are highly economical, making it the most popular.
기상합성법에서는 촉매금속의 사용이 필수적이며, 이중 Ni, Co 또는 Fe 등이 가장 많이 쓰이고 있으며, 각각의 촉매금속 입자는 하나의 씨드(seed)로 작용하여 탄소나노튜브가 형성되기 때문에, 촉매금속을 수 나노부터 수십 나노 크기의 입자로 형상화하는 것이 탄소나노튜브 합성의 핵심 기술이라 할 수 있다. In the gas phase synthesis method, the use of a catalyst metal is essential, of which Ni, Co or Fe are the most commonly used. Since each catalyst metal particle acts as a seed to form a carbon nanotube, the catalyst metal is used. Shaping particles from a few nanometers to tens of nanometers in size can be said to be the core technology for carbon nanotube synthesis.
이와 관련한 종래기술로서, 한국 공개특허공보 제10-2013-0078855호에서는 철(Fe), 코발트(Co) 및 망간(Mn)을 포함하는 금속촉매 성분과 상기 금속촉매를 함유하는 담지체로 구성된 담지촉매를 이용하여 표면결정성 및 전기전도성이 우수한 다중벽 탄소나노튜브를 제조하는 기술을 공지하였으며, 또한 한국 공개특허공보 제10-2010-0077422호에서는 코발트(Co), 바나듐(V), 알루미늄(Al) 및 불활성 다공성 지지체를 함유하는 다성분 금속 촉매 상에서 저급 포화 또는 불포화 탄화수소의 고온 분해를 통하여 기상 성장법으로 5~30 nm의 직경을 가지는 탄소나노튜브를 제조하는 기술에 대하여 개시하고 있다.As a prior art related to this, Korean Patent Publication No. 10-2013-0078855 discloses a supported catalyst consisting of a metal catalyst component containing iron (Fe), cobalt (Co), and manganese (Mn) and a support containing the metal catalyst. A technology for manufacturing multi-walled carbon nanotubes with excellent surface crystallinity and electrical conductivity using ) and a technology for producing carbon nanotubes with a diameter of 5 to 30 nm by vapor phase growth through high temperature decomposition of low-level saturated or unsaturated hydrocarbons on a multi-component metal catalyst containing an inert porous support.
여기서, 철(Fe), 코발트(Co) 및 망간(Mn) 등의 금속 촉매 성분을 담지하는 다공성 지지체로서 산화알루미늄, 산화마그네슘, 이산화규소 등을 사용하며, 여기서 산화 마그네슘의 다공성 지지체를 제조하기 위해 비특허문헌 1(M. Rezaei, M. Khajenoori, B. Nematollahi, Powder technology, 205(2011) pp. 112-116)에 공지된 방법은 Mg(NO3)2를 마그네슘 전구체로 사용하고, Block copolymer인 P123를 템플레이트로 사용하여 산화마그네슘 지지체를 제조하며, 다소 복잡한 공정으로 인하여 다공성의 산화마그네슘을 재현성 있게 제조하는 것이 어려우며, 또한 비특허문헌 2(A. Hanif, S. Dasgupta, A. Nanoti, Industrial & Engineering Chemistry Research, 55(2016), pp. 8070-8078)에 기재된 방법은 Mg(NO3)2 수화물을 400℃에서 진공 분위기하에서 소성하여 다공성의 산화마그네슘을 제조할 수 있어 상대적으로 제조 공정이 간단하나, 이를 이용해 작은 기공이 가장 잘 발달하여 높은 비표면적 값을 나타내는 제조된 다공성 산화마그네슘 지지체를 재현성있게 제조하는 것이 어렵다.한편, 메탄 가스는 지구온난화에 영향을 미치는 온실 가스로, 전 세계적으로 메탄 가스를 감축하려는 대책을 세우고 있으며, 이를 활용하는 연구도 진행되고 있다. 이러한 메탄을 활용하는 MCD(Methane Catalytic Decomposition)법은 고부가가치의 MWCNT 및 친환경 에너지인 수소 가스를 얻을 수 있어 저가의 반응물로부터 고부가가치의 생성물을 얻을 수 있다는 장점을 갖는다. Here, aluminum oxide, magnesium oxide, silicon dioxide, etc. are used as porous supports supporting metal catalyst components such as iron (Fe), cobalt (Co), and manganese (Mn), and here, to produce a porous support of magnesium oxide. The method known in Non-Patent Document 1 (M. Rezaei, M. Khajenoori, B. Nematollahi, Powder technology, 205 (2011) pp. 112-116) uses Mg(NO 3 ) 2 as a magnesium precursor and blocks copolymer. A magnesium oxide support is manufactured using phosphorus P123 as a template, and it is difficult to reproducibly manufacture porous magnesium oxide due to a somewhat complicated process. In addition, non-patent document 2 (A. Hanif, S. Dasgupta, A. Nanoti, Industrial & Engineering Chemistry Research, 55 (2016), pp. 8070-8078) can produce porous magnesium oxide by calcining Mg(NO 3 ) 2 hydrate in a vacuum atmosphere at 400°C, making the manufacturing process relatively simple. Although simple, it is difficult to reproducibly manufacture the prepared porous magnesium oxide support that exhibits high specific surface area values due to the best development of small pores using this method. Meanwhile, methane gas is a greenhouse gas that affects global warming, and is used worldwide. Measures are being taken to reduce methane gas, and research on utilizing this is also being conducted. The MCD (Methane Catalytic Decomposition) method using methane has the advantage of being able to obtain high value-added MWCNTs and hydrogen gas, an eco-friendly energy, and thus obtain high value-added products from low-cost reactants.
그러나, 전술한 합성법에 의해 제조된 탄소나노튜브는 여전히 저결정성 및 낮은 전도도 특성으로 인해 도전성 복합재 및 코팅재, 고성능 이차전지의 도전재 및 전극재로 사용하는데 어려움이 있다.However, carbon nanotubes manufactured by the above-described synthesis method still have difficulty in using them as conductive composites and coating materials, and as conductive materials and electrode materials for high-performance secondary batteries due to their low crystallinity and low conductivity characteristics.
이러한 문제점을 극복하기 위하여, MWCNT는 직경 크기를 작게 하거나, 벽의 개수를 적게 하여 탄소나노튜브의 전도성 및 결정성을 향상시킬 수 있다. 따라서, MWCNT 합성 과정에서 직경 크기가 작고 벽 수가 적은 MWCNT를 합성하는 것이 상업적으로 중요하며, MCD법을 통해 고전도성 및 고결정성의 MWCNT를 합성하기 위해서는 높은 활성을 갖는 촉매 제조가 중요하다.To overcome these problems, MWCNTs can improve the conductivity and crystallinity of carbon nanotubes by reducing the diameter size or reducing the number of walls. Therefore, in the MWCNT synthesis process, it is commercially important to synthesize MWCNTs with a small diameter and a small number of walls, and in order to synthesize MWCNTs with high conductivity and high crystallinity through the MCD method, it is important to prepare a catalyst with high activity.
본 발명의 주된 목적은 상술한 문제점을 해결하기 위한 것으로서, 전도성 및 결정성이 향상된 다중벽 탄소나노튜브(MWCNT)를 제조하기 위한 메탄 촉매적 분해 반응용 촉매 및 이를 이용하여 다중벽 탄소나노튜브(MWCNT) 및 수소를 생산하는 방법을 제공하는 것이다.The main purpose of the present invention is to solve the above-mentioned problems, including a catalyst for methane catalytic decomposition reaction to produce multi-walled carbon nanotubes (MWCNT) with improved conductivity and crystallinity, and a multi-walled carbon nanotube (MWCNT) using the same. To provide a method for producing MWCNT) and hydrogen.
상기와 같은 목적을 달성하기 위하여, 본 발명의 일 구현예는 (a) 탄산마그네슘(MgCO3)을 300 내지 700 ℃에서 소성하여 다공성의 산화마그네슘(MgO) 지지체를 제조하는 단계; (b) 금속 전구체를 용매에 용해시켜 금속 전구체 수용액을 제조하는 단계; 및 (c) 상기 금속 전구체 수용액에 상기 다공성의 산화마그네슘 지지체를 첨가한 후 200 내지 600 ℃에서 소성하여 담지촉매를 제조하는 단계;를 포함하는 것을 특징으로 하는 다중벽 탄소나노튜브 합성용 담지촉매의 제조방법을 제공한다.In order to achieve the above object, one embodiment of the present invention includes the steps of (a) calcining magnesium carbonate (MgCO3) at 300 to 700° C. to produce a porous magnesium oxide (MgO) support; (b) preparing a metal precursor aqueous solution by dissolving the metal precursor in a solvent; and (c) adding the porous magnesium oxide support to the aqueous metal precursor solution and then calcining at 200 to 600° C. to prepare a supported catalyst. Manufacturing method is provided.
본 발명의 바람직한 일 구현예에서, 상기 (a) 단계에서의 열처리 온도는 350 내지 450 ℃일 수 있다.In a preferred embodiment of the present invention, the heat treatment temperature in step (a) may be 350 to 450 °C.
본 발명의 바람직한 일 구현예에서, 상기 금속 전구체는 철(Fe), 코발트(Co), 망간(Mn) 및 몰리브덴(Mo) 중에서 선택되는 1종 이상의 금속을 포함할 수 있다.In a preferred embodiment of the present invention, the metal precursor may include one or more metals selected from iron (Fe), cobalt (Co), manganese (Mn), and molybdenum (Mo).
본 발명의 바람직한 일 구현예에서, 상기 금속 전구체는 코발트(Co) 및 몰리브덴(Mo)을 포함할 수 있다.In a preferred embodiment of the present invention, the metal precursor may include cobalt (Co) and molybdenum (Mo).
본 발명의 바람직한 일 구현예에서, 상기 다중벽 탄소나노튜브 합성용 담지촉매는 상기 코발트(Co)를 2 내지 30 wt% 함유하고, 상기 몰리브덴(Mo)은 2 내지 30 wt% 함유할 수 있다.In a preferred embodiment of the present invention, the supported catalyst for synthesizing multi-walled carbon nanotubes may contain 2 to 30 wt% of cobalt (Co) and 2 to 30 wt% of molybdenum (Mo).
본 발명의 바람직한 일 구현예에서, 상기 용매는 물, 알콜류, 또는 이들의 혼합물일 수 있다.In a preferred embodiment of the present invention, the solvent may be water, alcohol, or a mixture thereof.
또한, 본 발명의 다른 일 구현예는 상기 다중벽 탄소나노튜브 합성용 담지촉매의 제조방법으로 제조되고, 상기 담치촉매의 비표면적이 40 내지 200 m2/g인 것을 특징으로 하는 다중벽 탄소나노튜브 합성용 담지촉매를 제공한다.In addition, another embodiment of the present invention is a multi-walled carbon nanotube manufactured by the method for producing a supported catalyst for synthesizing multi-walled carbon nanotubes, wherein the supported catalyst has a specific surface area of 40 to 200 m 2 /g. A supported catalyst for tube synthesis is provided.
또한, 본 발명의 또 다른 일 구현예는 상기 다중벽 탄소나노튜브 합성용 담지촉매의 제조방법으로 제조되고, 상기 담치촉매의 비표면적이 150 내지 200 m2/g인 것을 특징으로 하는 다중벽 탄소나노튜브 합성용 담지촉매를 제공한다.In addition, another embodiment of the present invention is a multi-walled carbon produced by the method for producing a supported catalyst for synthesizing multi-walled carbon nanotubes, wherein the supported catalyst has a specific surface area of 150 to 200 m 2 /g. A supported catalyst for nanotube synthesis is provided.
또한, 본 발명의 또 다른 일 구현예는 (a) 상기 다중벽 탄소나노튜브 합성용 담지촉매를 열화학기상증착 장비에 장입하고, 650 내지 1100 ℃에서 수소 가스를 투입하여 담지 촉매를 환원시키는 단계; 및 (b) 650 내지 1100 ℃에서 탄화수소가스를 투입하여 다중벽 탄소나노튜브를 제조하는 방법을 제공한다.In addition, another embodiment of the present invention includes the steps of (a) loading the supported catalyst for multi-walled carbon nanotube synthesis into a thermochemical vapor deposition equipment and introducing hydrogen gas at 650 to 1100° C. to reduce the supported catalyst; and (b) providing a method of producing multi-walled carbon nanotubes by introducing hydrocarbon gas at 650 to 1100°C.
본 발명의 바람직한 일 구현예에서, 상기 탄화수소가스는 메탄, 에틸렌, 아세틸렌, LPG 또는 이들의 혼합가스일 수 있다.In a preferred embodiment of the present invention, the hydrocarbon gas may be methane, ethylene, acetylene, LPG, or a mixture thereof.
본 발명에 따른 메탄 촉매적 분해 반응용 촉매는 높은 수율로 다중벽 탄소나노튜브(MWCNT) 및 수소를 생산할 수 있으며, 제조된 다중벽 탄소나노튜브는 높은 에너지 밀도를 가져 현재 리튬이차전지의 양극재용 도전재로 사용되는 카본블랙을 대체하여 도전재의 사용량을 줄이고, 양극재의 함유량을 늘려 이차전지의 배터리 용량을 늘릴 수 있다.The catalyst for methane catalytic decomposition reaction according to the present invention can produce multi-walled carbon nanotubes (MWCNTs) and hydrogen in high yield, and the manufactured multi-walled carbon nanotubes have high energy density and are currently used as cathode materials for lithium secondary batteries. By replacing carbon black used as a conductive material, the amount of conductive material used can be reduced and the battery capacity of secondary batteries can be increased by increasing the content of the anode material.
따라서, 본 발명에 따른 다중벽 탄소나노튜브는 장수명 특성이 요구되는 전기 자동차, 휴대용 전자 기기의 배터리 용량을 개선시킬 수 있다.Therefore, the multi-walled carbon nanotube according to the present invention can improve the battery capacity of electric vehicles and portable electronic devices that require long life characteristics.
도 1은 본 발명의 (a) 비교예 1 및 (b) 실시예 1에 따른 담지촉매를 이용한 메탄의 촉매적 분해 반응에서 MWCNT의 생성 메커니즘을 나타낸 모식도이다.
도 2는 본 발명의 비교예 1, 실시예 1~3에 따른 Co25Mo25/MgO 담지촉매를 N2 adsorption-desorption 분석에 의해 측정된 (a) 압력에 따른 흡착량 및 (b) 기공 사이즈별 기공 부피를 나타낸 것이다.
도 3은 본 발명의 (a) 비교예 1 및 (b) 실시예 1에 따른 Co25Mo25/MgO 담지촉매의 전자주사현미경(SEM) 사진이다.
도 4는 본 발명의 비교예 1, 실시예 1~3에 따른 Co25Mo25/MgO 담지촉매의 열중량분석(TGA) 결과이다.
도 5는 본 발명의 비교예 1, 실시예 1~3에 따른 Co25Mo25/MgO 담지촉매를 이용한 메탄의 촉매적 분해 반응에서 시간에 따른 메탄의 전환률 및 수소의 생성률을 나타낸 그래프이다.
도 6은 본 발명의 비교예 1, 실시예 1~3에 따른 Co25Mo25/MgO 담지촉매를 이용한 메탄의 촉매적 분해 반응에서 생성된 MWCNT의 전자주사현미경(SEM) 사진과 MWCNT의 직경의 분포를 나타낸 것이다.
도 7은 본 발명의 비교예 1, 실시예 1~3에 따른 Co25Mo25/MgO 담지촉매를 이용한 메탄의 촉매적 분해 반응에서 생성된 MWCNT 및 상용 MWCNT의 라만 분석(Raman Spectroscopy) 결과이다.
도 8은 (a) 본 발명의 비교예 1, 실시예 1~3 에 따른 Co25Mo25/MgO 담지촉매를 이용한 메탄의 촉매적 분해 반응에서 생성된 MWCNT (b) Super P의 전기전도 특성을 측정한 결과이다.
도 9는 본 발명의 실시예 4~7에 따른 CoMo/MgO 담지촉매의 열중량분석(TGA) 결과이다.
도 10은 본 발명의 실시예 4~7에 따른 CoMo/MgO 담지촉매를 이용한 메탄의 촉매적 분해 반응에서 생성된 MWCNT의 라만 분석(Raman Spectroscopy) 결과이다.
도 11은 본 발명의 실시예 4~7에 따른 CoMo/MgO 담지촉매를 이용한 메탄의 촉매적 분해 반응에서 생성된 MWCNT의 전기전도 특성을 측정한 결과이다.Figure 1 is a schematic diagram showing the production mechanism of MWCNTs in the catalytic decomposition reaction of methane using a supported catalyst according to (a) Comparative Example 1 and (b) Example 1 of the present invention.
Figure 2 shows (a) adsorption amount according to pressure and (b) pore size measured by N2 adsorption-desorption analysis of the Co 25 Mo 25 /MgO supported catalyst according to Comparative Example 1 and Examples 1 to 3 of the present invention. It represents the pore volume.
Figure 3 is a scanning electron microscope (SEM) photograph of the Co 25 Mo 25 /MgO supported catalyst according to (a) Comparative Example 1 and (b) Example 1 of the present invention.
Figure 4 shows the results of thermogravimetric analysis (TGA) of the Co 25 Mo 25 /MgO supported catalyst according to Comparative Example 1 and Examples 1 to 3 of the present invention.
Figure 5 is a graph showing the conversion rate of methane and the production rate of hydrogen over time in the catalytic decomposition reaction of methane using the Co 25 Mo 25 /MgO supported catalyst according to Comparative Example 1 and Examples 1 to 3 of the present invention.
Figure 6 is a scanning electron microscope (SEM) photograph of MWCNTs produced in the catalytic decomposition reaction of methane using the Co 25 Mo 25 /MgO supported catalyst according to Comparative Example 1 and Examples 1 to 3 of the present invention and the diameter of the MWCNTs. It shows the distribution.
Figure 7 shows the results of Raman spectroscopy of MWCNTs and commercial MWCNTs produced in the catalytic decomposition reaction of methane using the Co 25 Mo 25 /MgO supported catalyst according to Comparative Example 1 and Examples 1 to 3 of the present invention.
Figure 8 shows the electrical conductivity characteristics of (a) MWCNTs produced in the catalytic decomposition reaction of methane using the Co 25 Mo 25 /MgO supported catalyst according to Comparative Example 1 and Examples 1 to 3 of the present invention (b) Super P. This is the result of measurement.
Figure 9 shows the results of thermogravimetric analysis (TGA) of the CoMo/MgO supported catalyst according to Examples 4 to 7 of the present invention.
Figure 10 shows the results of Raman spectroscopy of MWCNTs produced in the catalytic decomposition reaction of methane using a CoMo/MgO supported catalyst according to Examples 4 to 7 of the present invention.
Figure 11 shows the results of measuring the electrical conductivity characteristics of MWCNTs produced in the catalytic decomposition reaction of methane using a CoMo/MgO supported catalyst according to Examples 4 to 7 of the present invention.
다른 식으로 정의되지 않는 한, 본 명세서에서 사용된 모든 기술적 및 과학적 용어들은 본 발명이 속하는 기술분야에서 숙련된 전문가에 의해서 통상적으로 이해되는 것과 동일한 의미를 가진다. 일반적으로, 본 명세서에서 사용된 명명법은 본 기술분야에서 잘 알려져 있고 통상적으로 사용되는 것이다.Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. In general, the nomenclature used herein is well known and commonly used in the art.
본원 명세서 전체에서, 어떤 부분이 어떤 구성 요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성 요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있는 것을 의미한다.Throughout the specification of the present application, when a part "includes" a certain component, this means that it may further include other components rather than excluding other components unless specifically stated to the contrary.
본 발명은, (a) 탄산마그네슘(MgCO3)을 300 내지 700 ℃에서 소성하여 다공성의 산화마그네슘(MgO) 지지체를 제조하는 단계; (b) 금속 전구체를 용매에 용해시켜 금속 전구체 수용액을 제조하는 단계; 및 (c) 상기 금속 전구체 수용액에 상기 다공성의 산화마그네슘 지지체를 첨가한 후 200 내지 600 ℃에서 소성하여 담지촉매를 제조하는 단계;를 포함하는 것을 특징으로 하는 다중벽 탄소나노튜브 합성용 담지촉매의 제조방법를 제공한다.The present invention includes the steps of (a) calcining magnesium carbonate (MgCO 3 ) at 300 to 700° C. to produce a porous magnesium oxide (MgO) support; (b) preparing a metal precursor aqueous solution by dissolving the metal precursor in a solvent; and (c) adding the porous magnesium oxide support to the aqueous metal precursor solution and then calcining at 200 to 600° C. to prepare a supported catalyst. A manufacturing method is provided.
보다 구체적으로, 본 발명에 따른 다중벽 탄소나노튜브 합성용 담지촉매의 제조방법은 다공성의 산화마그네슘 지지체와 이에 담지된 이종 금속 촉매을 포함함으로써 촉매 반응 속도를 극대화하는 동시에, 촉매의 균일도와 분산성을 증가시킴으로써, 다중벽 탄소나노튜브 합성의 촉매 반응 속도를 극대화하고, 장기간 운전에서도 안정적인 촉매 성능을 가지는 다중벽 탄소나노튜브 합성용 담지촉매를 용이하게 제공할 수 있다.More specifically, the method for producing a supported catalyst for multi-walled carbon nanotube synthesis according to the present invention includes a porous magnesium oxide support and a heterogeneous metal catalyst supported thereon, thereby maximizing the catalytic reaction rate and improving the uniformity and dispersibility of the catalyst. By increasing the catalytic reaction rate for multi-walled carbon nanotube synthesis, it is possible to easily provide a supported catalyst for multi-walled carbon nanotube synthesis that has stable catalytic performance even during long-term operation.
이하 본 발명에 따른 다중벽 탄소나노튜브 합성용 담지촉매의 제조방을 첨부된 도면을 참조하여 보다 상세하게 설명하면 다음과 같다.Hereinafter, the manufacturing method of the supported catalyst for multi-walled carbon nanotube synthesis according to the present invention will be described in more detail with reference to the attached drawings.
도 1(a)은 non-porous 지지체를 포함하는 담지 촉매를 이용한 메탄의 촉매적 분해 반응에서 MWCNT의 생성 메커니즘을 나타낸 모식도이며, 도 1(b)는 각각 본 발명에 따른 담지촉매를 이용한 메탄의 촉매적 분해 반응에서 MWCNT의 생성 메커니즘을 나타낸 모식도이다.Figure 1(a) is a schematic diagram showing the production mechanism of MWCNTs in the catalytic decomposition reaction of methane using a supported catalyst containing a non-porous support, and Figure 1(b) is a schematic diagram showing the production mechanism of methane using a supported catalyst according to the present invention. This is a schematic diagram showing the production mechanism of MWCNTs in a catalytic decomposition reaction.
하기 도 1(b)에서 도시한 바와 같이, 본 발명에 따른 담지촉매는 다공성의 지지체 구조를 가지고 있어 활성 금속이 높은 분산성으로 담지되어 있다. 따라서, 본 발명에 따른 담지촉매는 높은 에너지 밀도를 가지는 직경이 작은 다중벽 탄소나노튜브(MWCNT)를 효과적으로 생산할 수 있다.As shown in Figure 1(b) below, the supported catalyst according to the present invention has a porous support structure, so the active metal is supported with high dispersibility. Therefore, the supported catalyst according to the present invention can effectively produce small-diameter multi-walled carbon nanotubes (MWCNTs) with high energy density.
먼저, 본 발명에 따른 담지촉매를 제조하기 위하여, 탄산마그네슘(MgCO3)을 300 내지 700 ℃에서 소성하여 다공성의 산화마그네슘(MgO) 지지체를 제조한다[(a) 단계].First, to prepare the supported catalyst according to the present invention, magnesium carbonate (MgCO 3 ) is calcined at 300 to 700° C. to prepare a porous magnesium oxide (MgO) support [step (a)].
일예로서, 상기 (a) 단계는 탄산마그네슘(MgCO3)을 2~10℃/min으로 승온하여, 300 내지 700 ℃의 온도에서 1~10 시간 동안 소성 과정을 통해 발달된 기공 구조를 갖는 산화마그네슘(MgO) 지지체를 제조한다.As an example, in step (a), magnesium carbonate (MgCO 3 ) is heated at 2 to 10° C./min, and magnesium oxide having a pore structure developed through a firing process is performed at a temperature of 300 to 700° C. for 1 to 10 hours. (MgO) support is prepared.
종래에는 Mg(NO3)2를 마그네슘 전구체로 사용하고, Block copolymer인 P123를 템플레이트로 사용하여 산화마그네슘 지지체를 제조하거나, Mg(NO3)2 수화물을 고온에서 소성하여 다공성의 산화마그네슘을 제조할 수 있으나, 이러한 제조 공정을 통하여 작은 기공이 가장 잘 발달하여 높은 비표면적 값을 나타내는 다공성 산화마그네슘 지지체를 재현성있게 제조하는 것이 어려운 문제점이 있었다.Previously, A magnesium oxide support can be manufactured using Mg(NO 3 ) 2 as a magnesium precursor and P123, a block copolymer, as a template, or porous magnesium oxide can be manufactured by calcining Mg(NO 3 ) 2 hydrate at high temperature. , there was a problem in reproducibly manufacturing a porous magnesium oxide support with the best development of small pores and a high specific surface area value through this manufacturing process.
그러나, 본원발명에서는 상기 (a) 단계에서 탄산마그네슘의 소성 온도를 적절히 제어함으로써 기공 구조가 잘 발달된 다공성의 산화마그네슘 지지체를 쉽게 제조할 수 있으며, 이러한 소성 공정은 복합한 제조 공정을 거칠 필요없이 적절한 소성 온도를 세팅하는 것만으로 다공성의 산화마그네슘 지지체를 재현성있게 제조할 수 있다.However, in the present invention, a porous magnesium oxide support with a well-developed pore structure can be easily manufactured by appropriately controlling the firing temperature of magnesium carbonate in step (a), and this firing process can be performed without the need for a complex manufacturing process. A porous magnesium oxide support can be manufactured reproducibly simply by setting an appropriate firing temperature.
일예로서, 상기 (a) 단계에서의 열처리 온도는 350 내지 450 ℃일 수 있으며, 350 내지 450 ℃의 온도범위에서 열처리할 때 산화마그네슘(MgO) 지지체의 기공이 가장 잘 발달하여 작은 기공 크기 및 높은 비표면적 값을 나타낸다.As an example, the heat treatment temperature in step (a) may be 350 to 450 ℃, and when heat treated in the temperature range of 350 to 450 ℃, the pores of the magnesium oxide (MgO) support are best developed, resulting in small pore size and high density. Indicates the specific surface area value.
이후, 금속 전구체를 용매에 용해시켜 금속 전구체 수용액을 제조한다[(b) 단계].Thereafter, the metal precursor is dissolved in a solvent to prepare an aqueous metal precursor solution [step (b)].
일예로서, 상기 금속 전구체는 철(Fe), 코발트(Co), 망간(Mn) 및 몰리브덴(Mo) 중에서 선택되는 1종 이상의 금속을 포함할 수 있으며, 바람직하게는 코발트(Co) 및 몰리브덴(Mo)을 포함할 수 있다.As an example, the metal precursor may include one or more metals selected from iron (Fe), cobalt (Co), manganese (Mn), and molybdenum (Mo), preferably cobalt (Co) and molybdenum (Mo). ) may include.
또한 일예로서, 상기 철(Fe) 전구체로는 FeCl2, FeCl3 등의 철 염화물; FeO, Fe2O3, Fe3O4 등의 철 산화물; Fe5C2, Fe3C 등의 철탄화물; Fe2N, Fe4N, Fe7N3 등의 철 질화물; Fe2SiO4, Fe2O3·SiO2 등의 철 규화물; 및 철 규산염 중에서 선택되는 어느 하나일 수 있다.Also, as an example, the iron (Fe) precursor includes iron chloride such as FeCl 2 and FeCl 3 ; iron oxides such as FeO, Fe 2 O 3 , and Fe 3 O 4 ; iron carbides such as Fe 5 C 2 and Fe 3 C; iron nitrides such as Fe 2 N, Fe 4 N, and Fe 7 N 3 ; iron silicides such as Fe 2 SiO 4 and Fe 2 O 3 ·SiO 2 ; and iron silicate.
또한 일예로서, 상기 코발트(Co) 전구체로는 질산코발트(Co(NO3)2·6H2O), 염화코발트(CoCl2), 및 아세트산코발트(Co(CH3COO)2)으로 중에서 선택되는 어느 하나일 수 있다.Also, as an example, the cobalt (Co) precursor is selected from cobalt nitrate (Co(NO 3 ) 2 ·6H 2 O), cobalt chloride (CoCl 2 ), and cobalt acetate (Co(CH 3 COO) 2 ). It could be any one.
또한 일예로서, 상기 망간(Mn) 전구체로는 황산망간(MnSO₄), 탄산망간(MnCO₃), 질산망간(Mn(NO3)2·6H2O), 아세트산망간(C4H6MnO4), 염화망간(MnCl₂) 중에서 선택되는 어느 하나일 수 있다.Also, as an example, the manganese (Mn) precursor includes manganese sulfate (MnSO₄), manganese carbonate (MnCO₃), manganese nitrate (Mn(NO 3 ) 2 ·6H 2 O), manganese acetate (C 4 H 6 MnO 4 ), It may be any one selected from manganese chloride (MnCl₂).
또한 일예로서, 상기 몰리브덴(Mo) 전구체로는 몰리브덴암모늄((NH4)6Mo7O24·4H2O)을 사용할 수 있다.Also, as an example, molybdenum ammonium ((NH 4 ) 6 Mo 7 O 24 ·4H 2 O) may be used as the molybdenum (Mo) precursor.
또한 일예로서, 다중벽 탄소나노튜브 합성용 담지촉매는 상기 코발트(Co)를 2 내지 30 wt% 함유하고, 상기 몰리브덴(Mo)을 2 내지 30 wt% 함유할 수 있다.Also, as an example, the supported catalyst for synthesizing multi-walled carbon nanotubes may contain 2 to 30 wt% of cobalt (Co) and 2 to 30 wt% of molybdenum (Mo).
이때, 촉매의 활성에 있어서 담지된 금속의 함침 농도가 중요한 변수이며, 코발트(Co) 또는 몰리브덴(Mo)의 함량이 2 wt% 미만인 경우에는 촉매 활성이 적어 촉매 반응 속도가 떨어지며, 안정적인 촉매 성능을 나타낼 수 없고, 30 wt%를 초과할 경우에는 직경이 크며, 에너지 밀도가 낮은 다중벽 탄소나노튜브이 생산되는 문제점이 발생한다.At this time, the impregnation concentration of the supported metal is an important variable in the activity of the catalyst. If the content of cobalt (Co) or molybdenum (Mo) is less than 2 wt%, the catalytic activity is low, the catalytic reaction speed is reduced, and stable catalytic performance is not achieved. It cannot be expressed, and if it exceeds 30 wt%, there is a problem of producing multi-walled carbon nanotubes with a large diameter and low energy density.
여기서, 상기 용매는 물, 알콜류, 또는 이들의 혼합물일 수 있다.Here, the solvent may be water, alcohol, or a mixture thereof.
이후, 상기 금속 전구체 수용액에 상기 (a) 단계에서 제조한 다공성의 산화마그네슘 지지체를 첨가한 후 200 내지 600 ℃에서 소성하여 담지촉매를 제조한다[(b) 단계].Thereafter, the porous magnesium oxide support prepared in step (a) is added to the metal precursor aqueous solution and then calcined at 200 to 600° C. to prepare a supported catalyst [step (b)].
상기 다공성의 산화마그네슘 지지체 내부 또는 외부에 침지된 금속 전구체는 200 ℃ 미만의 온도에서 금속 산화물로 변경되지 않으며, 지지체 내 존재하는 휘발성 물질의 제거가 잘 이루어지지 않는다. 반면, 상기 온도 범위가 600 ℃를 초과하는 경우에는 금속 산화물 입자들끼리 응집되어 금속 산화물 입자가 고르게 분산되지 않는 문제점이 발생한다.The metal precursor immersed inside or outside the porous magnesium oxide support is not changed into metal oxide at a temperature below 200° C., and volatile substances present in the support are not easily removed. On the other hand, when the temperature range exceeds 600°C, a problem occurs in which the metal oxide particles are not evenly dispersed due to agglomeration among the metal oxide particles.
구체적으로, 상기 금속 전구체 수용액에 상기 (a) 단계에서 제조한 다공성의 산화마그네슘 지지체를 첨가하여 금속 전구체가 함침된 촉매 담체 화합물을 건조킨 후 소성한다.Specifically, the porous magnesium oxide support prepared in step (a) is added to the metal precursor aqueous solution, the catalyst carrier compound impregnated with the metal precursor is dried, and then fired.
여기서, 상기 건조 공정은 금속 전구체가 함침된 촉매 담체 화합물을 공기 또는 불활성 분위기에서 50 내지 120 ℃의 온도에서 3 내지 20시간 동안 수행한다.Here, the drying process is performed on the catalyst carrier compound impregnated with the metal precursor at a temperature of 50 to 120° C. for 3 to 20 hours in air or an inert atmosphere.
이어서, 상기 건조 공정을 거친 촉매 담체 화합물의 소성 공정은 공기 또는 불활성 분위기에서 300 내지 600℃의 온도까지 1 ℃/min 이상의 승온 속도로 가열하여 수행할 수 있는데, 이러한 건조 및 소성 공정를 통해 촉매 담체에 함유된 수분 및 불순물이 제거되고, 열적 내구성 및 촉매 활성이 향상된다.Subsequently, the calcination process of the catalyst carrier compound that has undergone the drying process can be performed by heating the catalyst carrier compound in air or an inert atmosphere to a temperature of 300 to 600 ℃ at a temperature increase rate of 1 ℃/min or more. Through this drying and calcination process, the catalyst carrier compound Contained moisture and impurities are removed, and thermal durability and catalytic activity are improved.
또한, 본 발명은 상기 제조방법으로 제조되고, 다중벽 탄소나노튜브 합성용 담지촉매를 제공한다.In addition, the present invention provides a supported catalyst for synthesizing multi-walled carbon nanotubes, which is prepared by the above production method.
이때, 상기 담지촉매의 비표면적이 40 내지 200 m2/g일 수 있으며, 바람직하게는 150 내지 200 m2/g일 수 있다.At this time, the specific surface area of the supported catalyst may be 40 to 200 m 2 /g, and preferably 150 to 200 m 2 /g.
담지촉매의 비표면적이 200 m2/g를 초과하는 경우에는 마이크로 기공(micro pore)이 활발하게 생성되어 메탄의 촉매적 분해 반응에서 반응물의 흐름이 방해된다. 즉, 반응 중 메탄(반응물)의 흡착이나 분산(diffusion)이 어려워 메탄의 촉매적 분해 반응에 대한 촉매의 활성이 떨어질 뿐만 아니라, 생성물에 의해 쉽게 기공이 막혀 촉매의 불활성화(deactivation)가 빠르게 진행된다. 따라서, 마이크로 기공(micro pore)을 다량으로 포함하는 담지 촉매를 이용하여 메탄의 촉매적 분해 반응을 수행하면, 다중벽 탄소나노튜브(MWCNT)의 수율이 감소하는 문제점이 발생한다.If the specific surface area of the supported catalyst exceeds 200 m2/g, micro pores are actively generated, hindering the flow of reactants in the catalytic decomposition reaction of methane. In other words, it is difficult to adsorb or disperse methane (reactant) during the reaction, so not only does the catalyst's activity for the catalytic decomposition reaction of methane decrease, but the pores are easily blocked by the product, leading to rapid deactivation of the catalyst. do. Therefore, when a catalytic decomposition reaction of methane is performed using a supported catalyst containing a large amount of micro pores, a problem occurs in which the yield of multi-walled carbon nanotubes (MWCNTs) is reduced.
또한, 본 발명에 따른 다중벽 탄소나노튜브 합성용 담지촉매를 열화학기상증착 장비에 장입하고, 650 내지 1100 ℃에서 수소 가스를 투입하여 담지 촉매를 환원시키는 단계; (b) 650 내지 1100 ℃에서 탄화수소가스를 투입하여 다중벽 탄소나노튜브를 제조하는 방법을 제공한다.In addition, charging the supported catalyst for multi-walled carbon nanotube synthesis according to the present invention into a thermochemical vapor deposition equipment, and reducing the supported catalyst by introducing hydrogen gas at 650 to 1100 ° C.; (b) A method for producing multi-walled carbon nanotubes is provided by introducing hydrocarbon gas at 650 to 1100 ° C.
여기서, 상기 (a) 단계의 환원 공정은 담지 촉매의 제조 공정에서 금속 산화물로 제조된 담지 촉매를 환원시키기 위한 공정이며, 이때 환원 공정의 온도가 650 ℃ 미만인 경우에는 담지 촉매내 금속 산화물이 완전히 환원되지 않으므로 이후 탄화수소가스와의 반응((b)단계)에서 탄화수소가스의 분해반응이 발생하지 않으며, 반면 환원 공정의 온도가 1100 ℃를 초과하면 담지 촉매내 금속 성분의 소결 현상으로 인하여 촉매의 활성이 저하되는 문제점이 발생한다.Here, the reduction process in step (a) is a process for reducing the supported catalyst made of metal oxide in the supported catalyst manufacturing process. At this time, if the temperature of the reduction process is less than 650 ℃, the metal oxide in the supported catalyst is completely reduced. Therefore, no decomposition reaction of hydrocarbon gas occurs in the subsequent reaction with hydrocarbon gas (step (b)). On the other hand, if the temperature of the reduction process exceeds 1100 ℃, the activity of the catalyst is reduced due to sintering of the metal component in the supported catalyst. Problems with deterioration arise.
다중벽 탄소나노튜브는 열화학기상증착법(TCVD-thermal chemical vapor deposition)에 의하여 합성이 이루어질 수 있다,Multi-walled carbon nanotubes can be synthesized by thermal chemical vapor deposition (TCVD).
일 실시예로서, 본 발명에 따른 담지촉매를 세라믹 보트에 담아 상기 TCVD 장비에 두고, 상압조건에서, 650∼1,100 ℃, 바람직하게는 670∼950 ℃의 온도에서 담지촉매의 존재 하에 탄화수소가스를 투입하여 제조될 수 있다. As an example, the supported catalyst according to the present invention is placed in a ceramic boat and placed in the TCVD equipment, and hydrocarbon gas is introduced in the presence of the supported catalyst at a temperature of 650 to 1,100 ℃, preferably 670 to 950 ℃, under normal pressure conditions. It can be manufactured.
상기 탄화수소가스로는 메탄, 에틸렌, 아세틸렌, LPG 또는 이들의 혼합가스 등이 사용될 수 있으나 반드시 이에 제한되는 것은 아니며. 상기 탄화수소가스와 함께 수소가스가 투입될 수 있다.The hydrocarbon gas may be methane, ethylene, acetylene, LPG, or a mixture thereof, but is not necessarily limited thereto. Hydrogen gas may be introduced along with the hydrocarbon gas.
상기 수소가스는 담지촉매에 붙어 있는 산소를 환원시켜 고온에서 발생할 수 있는 탄소나노튜브의 분해를 미연에 방지하기 위한 것으로, 상기 탄화수소가스 및 수소가스의 공급시간은 20분 내지 70시간, 바람직하게는 30분 내지 1시간 동안 공급할 수 있다. 상기 탄화수소 및 수소가스는 각각 80 내지 300 sccm의 유량으로 공급할 수 있다.The hydrogen gas is used to reduce oxygen attached to the supported catalyst to prevent decomposition of carbon nanotubes that may occur at high temperatures. The supply time of the hydrocarbon gas and hydrogen gas is 20 minutes to 70 hours, preferably It can be supplied for 30 minutes to 1 hour. The hydrocarbon and hydrogen gas can each be supplied at a flow rate of 80 to 300 sccm.
이하, 구체적인 실시예를 통해 본 발명을 보다 구체적으로 설명한다. Hereinafter, the present invention will be described in more detail through specific examples.
제조예 1~3 : MgO 지지체의 합성Preparation Examples 1 to 3: Synthesis of MgO support
MgO의 전구체인 MgCO3을 5℃/min으로 승온하여, 400, 500, 그리고 600℃의 온도에서 2시간 동안 소성 과정을 통해 발달된 기공 구조를 갖는 MgO 지지체를 형성하였다.MgCO 3 , a precursor of MgO, was heated at 5°C/min and fired at temperatures of 400, 500, and 600°C for 2 hours to form an MgO support with a developed pore structure.
(℃)firing temperature
(℃)
(cm3/g)Pore Volume
( cm3 /g)
400℃ 이하의 온도에서는 MgO의 합성이 잘 이루어지지 않으며, 기공 구조가 발달되지 않는다. 400℃ 이상의 온도에서는 생성된 MgO 입자 간 뭉침 현상으로 인해 기공이 감소하는 것을 확인할 수 있으며, 600℃ 이상의 온도에서는 거의 없어지는 것을 확인할 수 있다.At temperatures below 400°C, MgO is not synthesized well and the pore structure is not developed. At temperatures above 400°C, it can be seen that pores are reduced due to agglomeration between the generated MgO particles, and at temperatures above 600°C, it can be seen that they almost disappear.
따라서, MgCO3는 400℃에서 2시간 동안 소성한 것이 기공이 가장 잘 발달한 MgO를 합성할 수 있는 온도로 나타났다.Therefore, firing MgCO 3 at 400°C for 2 hours was found to be the temperature at which MgO with the best pore development could be synthesized.
실시예 1~3 : CoExamples 1-3: Co 2525 MoMo 2525 /MgO 촉매의 제조Preparation of /MgO catalyst
상기 제조예 1~3에서 합성된 지지체 MgO에 금속을 담지하기 위해 함침법을 이용하였으며 금속은 Cobalt, Molybdenum을 이용하였다.An impregnation method was used to support metals on the support MgO synthesized in Preparation Examples 1 to 3, and cobalt and molybdenum were used as metals.
25wt% Cobalt, 25wt% Molybdenum을 MgO에 함침시키기 위해 300ml 증류수에 각각의 Cobalt와 Molybdenum 전구체인 Co(NO3)2·6H2O, (NH4)6Mo7O24·4H2O 을 5.1g, 1.9g 용해시켰다. 이후에 합성된 MgO 3g을 첨가한 후 회전증발농축기를 이용하여 Cobalt와 Molybdenum을 담지하였다.To impregnate 25wt% Cobalt and 25wt% Molybdenum into MgO, 5.1g of Cobalt and Molybdenum precursors, Co(NO 3 ) 2 ·6H 2 O, (NH 4 ) 6 Mo 7 O 24 4H 2 O, were added to 300 ml of distilled water. , 1.9g was dissolved. Afterwards, 3g of synthesized MgO was added, and then cobalt and molybdenum were supported using a rotary evaporator.
80℃의 오븐에서 12시간 건조 후, 전기로를 이용하여 400℃에서 4시간동안 소성하여 촉매를 제조하였다.After drying in an oven at 80°C for 12 hours, the catalyst was prepared by baking at 400°C for 4 hours using an electric furnace.
실시예 4~7 : CoMo/MgO 촉매의 제조Examples 4-7: Preparation of CoMo/MgO catalyst
상기 제조예 1에서 합성된 지지체 MgO에 금속을 담지하기 위해 함침법을 이용하였으며 금속은 Cobalt, Molybdenum을 이용하였다.An impregnation method was used to support metal on the support MgO synthesized in Preparation Example 1, and cobalt and molybdenum were used as metals.
25wt% Cobalt, 5, 10, 15, 20wt% Molybdenum을 MgO에 함침시키기 위해 300ml 증류수에 각각의 Cobalt와 Molybdenum 전구체인 Co(NO3)2·6H2O, (NH4)6Mo7O24·4H2O 을 각각 용해시켰다. 이후에 합성된 MgO 3g을 첨가한 후 회전증발농축기를 이용하여 Cobalt와 Molybdenum을 담지하였다.To impregnate 25wt% Cobalt, 5, 10, 15, and 20wt% Molybdenum into MgO, each Cobalt and Molybdenum precursor, Co(NO 3 ) 2 ·6H 2 O, (NH 4 ) 6 Mo 7 O 24 ·, was added to 300 ml distilled water. 4H 2 O was dissolved respectively. Afterwards, 3g of synthesized MgO was added, and then cobalt and molybdenum were supported using a rotary evaporator.
80℃의 오븐에서 12시간 건조 후, 전기로를 이용하여 400℃에서 4시간동안 소성하여 촉매를 제조하였다.After drying in an oven at 80°C for 12 hours, the catalyst was prepared by baking at 400°C for 4 hours using an electric furnace.
실험예 1 : 메탄의 촉매적 분해 반응Experimental Example 1: Catalytic decomposition reaction of methane
쿼츠 튜브(길이 120cm, 내경 6cm) 내부에 0.2g의 촉매를 쿼츠 보트 위에 올린 후에 반응을 진행하였다.Inside the quartz tube (length 120 cm, inner diameter 6 cm), 0.2 g of catalyst was placed on the quartz boat, and then the reaction proceeded.
Ar 100ml/min을 흘려주며 10℃/min으로 승온하여 800℃에 도달한 후, H2:Ar (20ml:80ml) 가스를 30분동안 흘려주어 금속을 환원시켜 주었다. 이후 40분동안 Ar 100ml/min을 흘려주어 불활성 상태를 만들어준 후, CH4 50ml/min으로 2시간 동안 흘려주어 MCD 반응을 진행하였다.After flowing Ar 100ml/min and raising the temperature at 10℃/min to reach 800℃, H2:Ar (20ml:80ml) gas was flowed for 30 minutes to reduce the metal. Afterwards, Ar 100ml/min was flowed for 40 minutes to make it inert, and CH4 50ml/min was flowed for 2 hours to proceed with the MCD reaction.
실험예 2: NExperimental Example 2: N 22 adsorption-desorption 분석 adsorption-desorption analysis
촉매를 473K에서 8시간 동안 열처리를 한 후에, 장비 TRISTAR 3020를 통해서 77K에서 N2 가스를 주입하여 반응을 진행하였고, 분석된 결과는 BET 식을 통해서 계산하였다.After the catalyst was heat treated at 473K for 8 hours, the reaction was performed by injecting N 2 gas at 77K through equipment TRISTAR 3020, and the analyzed results were calculated using the BET equation.
하기 도 2에서 도시한 바와 같이, 본 발명에 따른 실시예 1~3의 Co25Mo25/MgO 담지촉매는 비교예 1의 촉매에 비하여 높은 질소 흡착량을 보여주며, 또한 기공 사이즈가 상대적으로 작게 나타난 것을 확인하였다.As shown in Figure 2 below, the Co 25 Mo 25 /MgO supported catalyst of Examples 1 to 3 according to the present invention shows a higher nitrogen adsorption amount than the catalyst of Comparative Example 1, and also has a relatively small pore size. It was confirmed that it appeared.
실험예 3: 촉매의 외관 관찰Experimental Example 3: Observation of the appearance of the catalyst
장비 Libra 200 MC TEM를 이용하여 200kV의 가속전압으로 촉매를 관찰하였다.The catalyst was observed at an acceleration voltage of 200 kV using the equipment Libra 200 MC TEM.
하기 도 3에서 도시한 바와 같이, 본 발명에 따른 실시예 1의 Co25Mo25/MgO 담지촉매는 비교예 1의 촉매에 비하여 기공이 형성이 더 발달한 것을 확인하였다.As shown in Figure 3 below, it was confirmed that the Co 25 Mo 25 /MgO supported catalyst of Example 1 according to the present invention had more developed pore formation than the catalyst of Comparative Example 1.
실험예 4: 열중량분석(TGA)Experimental Example 4: Thermogravimetric Analysis (TGA)
장비 Thermo plus EVO Ⅱ를 통해서 air 분위기 하 5℃/min으로 900℃까지 승온하여 나타낸 분석 결과를 아래의 도 4에 나타내었다.The analysis results obtained by raising the temperature to 900°C at 5°C/min in an air atmosphere using equipment Thermo plus EVO II are shown in Figure 4 below.
하기 도 4 및 도 9에서 도시한 바와 같이, 본 발명에 따른 실시예 1~7의 CoMo/MgO 담지촉매는 비교예 1의 촉매에 비하여 탄소나노튜브가 높은 비율로 형성된 것을 확인하였다.As shown in Figures 4 and 9 below, it was confirmed that carbon nanotubes were formed at a higher rate in the CoMo/MgO supported catalysts of Examples 1 to 7 according to the present invention compared to the catalyst of Comparative Example 1.
실험예 5: 가스 크로마토그래피Experimental Example 5: Gas Chromatography
장비 YL6500 GC를 이용하였으며, N2, H2, CH4를 분석할 수 있는 thermal conductivity detector(TCD)와 packed column(ShinCarbon ST 80/100,RESTEK)을 이용하여 분석한 결과를 아래의 도 5에 나타내었다.Equipment YL6500 GC was used, and the results of analysis using a thermal conductivity detector (TCD) and packed column (ShinCarbon ST 80/100, RESTEK) capable of analyzing N 2 , H 2 , and CH 4 are shown in Figure 5 below. indicated.
하기 도 5에서 도시한 바와 같이, 본 발명에 따른 실시예 1~3의 Co25Mo25/MgO 담지촉매는 비교예 1의 촉매에 비하여 메탄의 촉매적 분해 반응에서 시간에 따라 촉매 활성이 양호하게 유지되었으며, 높은 메탄의 전환률을 나타내는 것을 확인하였다.As shown in Figure 5 below, the Co 25 Mo 25 /MgO supported catalyst of Examples 1 to 3 according to the present invention showed good catalytic activity over time in the catalytic decomposition reaction of methane compared to the catalyst of Comparative Example 1. It was confirmed that it was maintained and showed a high methane conversion rate.
실험예 6: 생성물의 외관 관찰Experimental Example 6: Observation of the appearance of the product
장비 Libra 200 MC TEM를 이용하여 200kV의 가속전압에서 관찰한 탄소나노튜브 이미지와 응용 프로그램 Image J를 이용하여 100개의 CNT 직경의 평균 값을 아래의 도 6에 나타내었다.The carbon nanotube image observed at an acceleration voltage of 200 kV using the Libra 200 MC TEM equipment and the average value of the diameter of 100 CNTs using the application Image J are shown in Figure 6 below.
하기 도 6에서 도시한 바와 같이, 본 발명에 따른 실시예 1~3의 Co25Mo25/MgO 담지촉매는 비교예 1의 촉매에 비하여 메탄의 촉매적 분해 반응에서 생성된 MWCNT의 MWCNT의 직경이 작은 것으로 확인되었다.As shown in FIG. 6 below, the Co 25 Mo 25 /MgO supported catalyst of Examples 1 to 3 according to the present invention has a diameter of MWCNT produced in the catalytic decomposition reaction of methane compared to the catalyst of Comparative Example 1. It was confirmed to be small.
실험예 7: 라만 분석Experimental Example 7: Raman analysis
장비 Nanophoton Ramanforce를 이용하여 분석을 진행하였다. 분석에 이용된 파장은 532.04nm이며, 슬릿은 50㎛의 폭을 갖는 것을 사용하였다.또한 결정성의 경우 1350 cm-1에서 나타나는 D band peak와 1580 cm-1에서 나타나는 G band peak의 강도 비율을 통해 나타내었다.Analysis was performed using equipment Nanophoton Ramanforce. The wavelength used for analysis was 532.04nm, and the slit had a width of 50㎛. In addition, in the case of crystallinity, the intensity ratio of the D band peak appearing at 1350 cm -1 and the G band peak appearing at 1580 cm -1 indicated.
하기 도 7 및 도 10에서 도시한 바와 같이, 본 발명에 따른 실시예 1~3의 CoMo/MgO 담지촉매를 이용한 메탄의 촉매적 분해 반응에서 생성된 MWCNT는 높은 결정성을 나타내었으며, 상용 MWCNT의 결정성보다 우수한 값을 나타내는 것을 확인하였다.As shown in Figures 7 and 10 below, MWCNTs produced in the catalytic decomposition reaction of methane using the CoMo/MgO supported catalyst of Examples 1 to 3 according to the present invention showed high crystallinity and were comparable to those of commercial MWCNTs. It was confirmed that it showed a value superior to crystallinity.
실험예 8: 전기전도도 분석Experimental Example 8: Electrical conductivity analysis
장비 (HPRM-FA2, HANtech Co. Ltd, Korea)를 이용하였으며, 2000kgf 하중에서의 전기전도도를 나타내었다.Equipment (HPRM-FA2, HANtech Co. Ltd, Korea) was used, and electrical conductivity was shown at a load of 2000 kgf.
하기 도 8 및 도 11에서 도시한 바와 같이, 본 발명에 따른 실시예 1~7의 CoMo/MgO 담지촉매를 이용한 메탄의 촉매적 분해 반응에서 생성된 MWCNT는 비교적 높은 전기 전도도 특성을 나타내는 것을 확인하였다.As shown in Figures 8 and 11 below, it was confirmed that MWCNTs produced in the catalytic decomposition reaction of methane using the CoMo/MgO supported catalyst of Examples 1 to 7 according to the present invention exhibit relatively high electrical conductivity characteristics. .
이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는 바, 당업계의 통상의 지식을 가진 자에게 있어서 이러한 구체적 기술은 단지 바람직한 실시양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서, 본 발명의 실질적은 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다. As the specific parts of the present invention have been described in detail above, it is clear to those skilled in the art that these specific techniques are merely preferred embodiments and do not limit the scope of the present invention. will be. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.
Claims (10)
(b) 금속 전구체를 용매에 용해시켜 금속 전구체 수용액을 제조하는 단계;
(c) 상기 금속 전구체 수용액에 상기 다공성의 산화마그네슘 지지체를 첨가한 후 200 내지 600 ℃에서 소성하여 담지촉매를 제조하는 단계;를 포함하는 것을 특징으로 하는 다중벽 탄소나노튜브 합성용 담지촉매의 제조방법.
(a) producing a porous magnesium oxide (MgO) support by calcining magnesium carbonate (MgCO3) at 300 to 700°C;
(b) preparing a metal precursor aqueous solution by dissolving the metal precursor in a solvent;
(c) adding the porous magnesium oxide support to the aqueous metal precursor solution and then calcining at 200 to 600° C. to produce a supported catalyst; Preparation of a supported catalyst for multi-walled carbon nanotube synthesis, comprising: method.
상기 (a) 단계에서의 열처리 온도는 350 내지 450 ℃인 것을 특징으로 하는 다중벽 탄소나노튜브 합성용 담지촉매의 제조방법.
According to paragraph 1,
A method for producing a supported catalyst for multi-walled carbon nanotube synthesis, characterized in that the heat treatment temperature in step (a) is 350 to 450 ° C.
상기 금속 전구체는 철(Fe), 코발트(Co), 망간(Mn) 및 몰리브덴(Mo) 중에서 선택되는 1종 이상의 금속을 포함하는 것을 특징으로 하는 다중벽 탄소나노튜브 합성용 담지촉매의 제조방법.
According to paragraph 1,
A method for producing a supported catalyst for multi-walled carbon nanotube synthesis, wherein the metal precursor contains one or more metals selected from iron (Fe), cobalt (Co), manganese (Mn), and molybdenum (Mo).
상기 금속 전구체는 코발트(Co) 및 몰리브덴(Mo)을 포함하는 것을 특징으로 하는 다중벽 탄소나노튜브 합성용 담지촉매의 제조방법.
According to paragraph 1,
A method for producing a supported catalyst for multi-walled carbon nanotube synthesis, wherein the metal precursor contains cobalt (Co) and molybdenum (Mo).
상기 다중벽 탄소나노튜브 합성용 담지촉매는 상기 코발트(Co)를 2 내지 30 wt% 함유하고, 상기 몰리브덴(Mo)은 2 내지 30 wt% 함유하는 것을 특징으로 하는 다중벽 탄소나노튜브 합성용 담지촉매의 제조방법.
According to paragraph 4,
The supported catalyst for multi-walled carbon nanotube synthesis contains 2 to 30 wt% of cobalt (Co) and 2 to 30 wt% of molybdenum (Mo). Method for producing catalyst.
상기 용매는 물, 알콜류, 또는 이들의 혼합물인 것을 특징으로 하는 다중벽 탄소나노튜브 합성용 담지촉매의 제조방법.
According to paragraph 1,
A method for producing a supported catalyst for multi-walled carbon nanotube synthesis, wherein the solvent is water, alcohol, or a mixture thereof.
상기 담치촉매의 비표면적이 40 내지 200 m2/g인 것을 특징으로 하는 다중벽 탄소나노튜브 합성용 담지촉매.
Manufactured by the manufacturing method of any one of claims 1 to 5,
A supported catalyst for multi-walled carbon nanotube synthesis, characterized in that the specific surface area of the supported catalyst is 40 to 200 m 2 /g.
상기 담치촉매의 비표면적이 150 내지 200 m2/g인 것을 특징으로 하는 다중벽 탄소나노튜브 합성용 담지촉매.
Manufactured by the manufacturing method of any one of claims 1 to 5,
A supported catalyst for multi-walled carbon nanotube synthesis, characterized in that the specific surface area of the supported catalyst is 150 to 200 m 2 /g.
(b) 650 내지 1100 ℃에서 탄화수소가스를 투입하여 다중벽 탄소나노튜브를 제조하는 방법.
(a) charging the supported catalyst of paragraph 7 into a thermal chemical vapor deposition equipment and reducing the supported catalyst by introducing hydrogen gas at 650 to 1100°C;
(b) A method of producing multi-walled carbon nanotubes by introducing hydrocarbon gas at 650 to 1100 °C.
상기 탄화수소가스는 메탄, 에틸렌, 아세틸렌, LPG 또는 이들의 혼합가스인 것을 특징으로 하는 다중벽 탄소나노튜브를 제조하는 방법.According to clause 9,
A method for producing multi-walled carbon nanotubes, wherein the hydrocarbon gas is methane, ethylene, acetylene, LPG, or a mixture thereof.
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| KR20130078855A (en) | 2011-12-31 | 2013-07-10 | 제일모직주식회사 | Supported catalyst for synthesizing multi-wall carbon nanotube having an excellent crystallinity and method for preparing the same |
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| KR20100077422A (en) | 2008-12-29 | 2010-07-08 | 금호석유화학 주식회사 | Catalyst compositions for preparing carbon nanotube |
| KR20130078855A (en) | 2011-12-31 | 2013-07-10 | 제일모직주식회사 | Supported catalyst for synthesizing multi-wall carbon nanotube having an excellent crystallinity and method for preparing the same |
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