KR20070082141A - Process for preparing catalyst for synthesis of carbon nanotubes - Google Patents
Process for preparing catalyst for synthesis of carbon nanotubes Download PDFInfo
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- KR20070082141A KR20070082141A KR1020060014550A KR20060014550A KR20070082141A KR 20070082141 A KR20070082141 A KR 20070082141A KR 1020060014550 A KR1020060014550 A KR 1020060014550A KR 20060014550 A KR20060014550 A KR 20060014550A KR 20070082141 A KR20070082141 A KR 20070082141A
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- transition metal
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- solid oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 16
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title abstract description 14
- 230000015572 biosynthetic process Effects 0.000 title description 3
- 238000003786 synthesis reaction Methods 0.000 title description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 34
- 150000003624 transition metals Chemical class 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 238000005118 spray pyrolysis Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 239000011733 molybdenum Substances 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 4
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- 239000010937 tungsten Substances 0.000 claims abstract description 4
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- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 238000000265 homogenisation Methods 0.000 claims description 2
- -1 iron carbonyl Chemical compound 0.000 claims description 2
- 229940087654 iron carbonyl Drugs 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000002923 metal particle Substances 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
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- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 239000010949 copper Substances 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
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- 150000002605 large molecules Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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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
- B01J37/0201—Impregnation
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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
- 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
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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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
- 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
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- B01J35/40—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
Description
도 1은 본 발명에 따른 촉매금속 제조공정에 사용되는 분무열분해 장치의 개략도이고,1 is a schematic view of the spray pyrolysis apparatus used in the catalytic metal production process according to the present invention,
도 2는 본 발명에 따른 촉매금속 제조공정에 사용되는 연속형 분무열분해 장치의 개략도이고,2 is a schematic diagram of a continuous spray pyrolysis apparatus used in the catalytic metal production process according to the present invention,
도 3은 실시예 1에서 얻어진 담체 표면에 고착된 촉매입자의 주사전자현미경 사진이고,3 is a scanning electron micrograph of the catalyst particles fixed on the surface of the carrier obtained in Example 1,
도 4는 실시예 1에서 얻어진 담체 표면에 고착된 촉매입자의 투과전자현미경 사진이다.4 is a transmission electron micrograph of the catalyst particles fixed on the surface of the carrier obtained in Example 1.
<도면의 부호에 대한 간단한 설명><Short description of the symbols in the drawings>
1: 전기히터, 2: 반응챔버, 3: 필터, 4: 생성물, 5: 가스 배기구, 6: 촉매액 주입구, 7: 질소가스 주입구, 8: 스프레이 노즐, 9: 촉매지지체 슬러리, 10: 전이금속 용액, 11: 유량조절기, 12: 균질화기DESCRIPTION OF SYMBOLS 1: Electric heater, 2: Reaction chamber, 3: Filter, 4: Product, 5: Gas exhaust port, 6: Catalyst liquid inlet, 7: Nitrogen gas inlet, 8: Spray nozzle, 9: Catalyst support slurry, 10: Transition metal Solution, 11: flow regulator, 12: homogenizer
본 발명은 탄소나노튜브 합성용 촉매의 제조방법에 관한 것이다.The present invention relates to a method for preparing a catalyst for synthesizing carbon nanotubes.
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. 원통형을 이루는 결합 구조에 따라 일부러 불순물을 넣지 않아도 튜브와 튜브가 상호 작용하면서 도체에서 반도체로 변한다. 말려진 형태에 따라서 단층벽 나노튜브(single walled nanotube, SWNT), 다중벽 나노튜브(multi-walled nanotube, MWNT), 다발형 나노튜브(rope nanotube)로 구분되기도 한다. Carbon nanotubes are hexagonal honeycomb graphite surfaces, in which one carbon atom is bonded to three other carbon atoms, which are rounded to a nano-sized diameter, and are large molecules having unique physical properties according to their size and shape. It is hollow, lightweight and has good electrical conductivity as copper, thermal conductivity as good as diamond and tensile strength as steel. According to the cylindrical coupling structure, the tube and the tube interact with each other and change from conductor to semiconductor without intentionally adding impurities. Depending on the shape of the roll, it may be divided into single walled nanotubes (SWNTs), multi-walled nanotubes (MWNTs), and rope nanotubes.
이러한 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.Such carbon nanotubes may be generally manufactured by an electric discharge method, a laser deposition method, a plasma chemical vapor deposition method, a thermochemical vapor deposition method, a gas phase synthesis method, and an electrolysis method, and in the case of the double gas phase synthesis method, carbon in a reactor without using a substrate is used. Since it forms a deposit of carbon nanotubes by directly supplying and reacting a gas containing a catalyst metal with a catalyst metal, it is possible to synthesize a large amount of high purity carbon nanotubes, but it is also very economical and is attracting the most attention.
따라서, 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. 따라서, 탄소나노튜브 합성에 필수적인 촉매금속의 제조방법에 대한 여러 연구가 진행되고 있다.Therefore, in the gas phase synthesis method, the use of a catalyst metal is essential. Among them, Ni, Co, or Fe is most frequently used, and each catalyst metal particle acts as a seed to form carbon nanotubes. Shaping metal from particles of several nanometers to several tens of nanometers in size is the core technology of carbon nanotube synthesis. Therefore, various studies on the preparation method of the catalytic metal which is essential for the synthesis of carbon nanotubes have been conducted.
지금까지 보고된 촉매금속의 제조방법으로는, 예를 들면 촉매제 담체 및 촉매금속 또는 금속 조합을 용액 상태에서 pH, 온도 및/또는 조성물을 변화시켜 공침시킨 후 침전물을 분리하여 공기 또는 다른 가스 환경에서 가열 처리하는 방법, 미립자 담체물질과 촉매 금속을 함유하는 현탁액을 건조 또는 증발시키는 초기 함침법, 제올라이트와 같은 양이온 미립자 담체물질을 촉매 금속염과 혼합하여 이온화 시킨 후 수소 또는 다른 환원수단을 이용하여 고온에서 금속입자로 환원하는 방법, 촉매금속과 마그네시아, 알루미나, 실리카 등의 고체 산화물 담체물질을 혼합된 상태에서 연소시키는 방법, 및 촉매금속 전구체 용액을 분무/미세화하여 연소시키는 방법 등이 보고되고 있으나(대한민국 특허공개 제2003-91016호, 제2003-8842호, 제2005-72056호, 제2001-79867호, 제2002-84087호, 제2004-31714호 및 제2004-82950호; 및 미국특허공개 제2004/0162216 A1호), 대부분 제조된 촉매의 평균입경이 0.1 내지 수 ㎛로 미세화에 한계가 있거나, 촉매의 대량생산이 곤란하거나 경제성이 떨어지는 등 문제가 있었다. As a method for producing a catalyst metal reported so far, for example, the catalyst carrier and the catalyst metal or metal combination are co-precipitated by changing the pH, temperature and / or composition in a solution state, and then the precipitate is separated to provide an air or other gas environment. Method of heat treatment, initial impregnation method of drying or evaporating suspension containing particulate carrier material and catalyst metal, cationic particulate carrier material such as zeolite is mixed with catalyst metal salt and ionized, followed by hydrogen or other reducing means at high temperature. Reduction of metal particles, combustion of catalytic metals and solid oxide carrier materials such as magnesia, alumina, and silica in a mixed state, and combustion of the catalyst metal precursor solution by spraying / micronizing have been reported. Patent Publication Nos. 2003-91016, 2003-8842, 2005-72056, 2001-79867, Nos. 2002-84087, 2004-31714 and 2004-82950; and US Patent Publication No. 2004/0162216 A1), most of the catalysts produced have an average particle diameter of 0.1 to a few micrometers and have a limited micronization, or There was a problem such as difficult to mass-produce or low economic feasibility.
이에, 본 발명의 목적은 평균입경이 100 nm 이하인, 탄소나노튜브 합성용 금 속촉매를 대량으로 제조할 수 있는 방법을 제공하는 것이다.Accordingly, an object of the present invention is to provide a method for producing a large amount of metal catalyst for synthesizing carbon nanotubes having an average particle diameter of 100 nm or less.
상기 목적에 따라, 본 발명에서는 1) 전이금속 전구체를 용매에 용해시켜 전이금속 전구체 용액을 제조하는 단계; 2) 단계 1) 에서 얻어진 전이금속 전구체 용액 내 전이금속 전구체를 고체 산화물 담체 표면에 흡착시키는 단계; 및 3) 단계 2) 에서 생성된 복합체 용액을 분무 열분해시켜 전이금속을 담체 표면에 고착시키는 단계를 포함하는, 탄소나노튜브 합성용 금속촉매의 제조방법을 제공한다. According to the above object, in the present invention 1) preparing a transition metal precursor solution by dissolving the transition metal precursor in a solvent; 2) adsorbing the transition metal precursor in the transition metal precursor solution obtained in step 1) to the surface of the solid oxide carrier; And 3) spray pyrolyzing the complex solution produced in step 2) to fix the transition metal on the surface of the carrier.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 제조방법은, 기존 분무 열분해를 이용한 탄소나노튜브 합성용 촉매 제조방법에서 단순히 전이금속 전구체 용액만을 사용하던 것과는 달리, 분무 열분해 공정 중 열에 의한 전이금속 입자의 응집을 방지하기 위해 고체산화물 담체 표면에 전이금속 전구체를 흡착시킨 복합체 용액 상태로 분무 열분해를 수행하여 전이금속을 담체 표면에 고착시켜 100 ㎚ 이하의 평균입경을 갖는 금속촉매를 대량으로 생산할 수 있다는 것을 특징으로 한다.Unlike the conventional method of preparing a catalyst for synthesizing carbon nanotubes using spray pyrolysis, the manufacturing method of the present invention uses a solid oxide carrier to prevent aggregation of transition metal particles by heat during spray pyrolysis. Spray pyrolysis is carried out in a complex solution state in which a transition metal precursor is adsorbed on a surface, thereby adhering the transition metal to a carrier surface, thereby producing a large amount of a metal catalyst having an average particle diameter of 100 nm or less.
상기 단계 1에서는 전이금속 전구체를 용매에 용해시켜 전이금속 전구체 용액을 제조하게 되는데, 이때 전이금속 전구체로는 철, 니켈, 코발트, 몰리브덴, 팔라듐, 텅스텐, 크롬, 이리듐 및 이들의 혼합물 등에서 선택된 금속의 염이 사용될 수 있으며, 바람직하게는 질산철(iron nitrate), 철카보닐(iron carbonyl), 질산니 켈(nickel nitrate), 질산코발트(cobalt nitrate) 및 몰리브덴산(molybdic acid) 등이 사용될 수 있다. 또한, 용매로는 물, 에탄올, 아세톤, 벤젠 및 신나 등을 사용할 수 있다. 또한, 전이금속 전구체는 용액 내 5 내지 40 중량%, 바람직하게는 20 내지 30 중량%로 포함될 수 있다.In step 1, the transition metal precursor is dissolved in a solvent to prepare a transition metal precursor solution, wherein the transition metal precursor includes a metal selected from iron, nickel, cobalt, molybdenum, palladium, tungsten, chromium, iridium and mixtures thereof. Salts may be used, preferably iron nitrate, iron carbonyl, nickel nitrate, cobalt nitrate and molybdic acid may be used. . As the solvent, water, ethanol, acetone, benzene, thinner and the like can be used. In addition, the transition metal precursor may be included in 5 to 40% by weight, preferably 20 to 30% by weight in the solution.
단계 2에서 사용되는 고체산화물 담체는 분무 열분해 공정 중 전이금속 입자들 간의 응집을 방지하여 촉매 입경이 커지는 것을 저해하는 역할을 하며, 이러한 담체로는 제올라이트, 실리카, 마그네시아, 지르코니아 및 이들의 혼합물 중에서 선택된 것을 사용할 수 있다.The solid oxide carrier used in
단계 2에서 고체 산화물 담체에 전이금속 전구체를 흡착시키는 방법으로는, 예를 들면 단계 1)에서 얻어진 전이금속 전구체 용액에 담체를 첨가시켜 수행될 수 있으며, 이때 고체산화물 담체와 전이금속 전구체의 혼합 중량비는 1:0.5 내지 4, 바람직하게는 1:1 내지 2 범위일 수 있다. 또한, 단계 2에서 얻어진 복합체 용액 중 고체산화물 담체의 농도는 2 내지 20중량%, 바람직하게는 5 내지 10중량% 범위일 수 있으며, 이러한 복합체 용액 중에는 담체 입자 표면에 금속 전구체가 상당량 흡착되어 형성된 복합체와 함께 일부 흡착되지 않은 금속 전구체가 잔존할 수 있다.As a method of adsorbing the transition metal precursor to the solid oxide carrier in
또한, 본 발명의 단계 2에서는, 흡착효과를 더욱 향상시키기 위해 얻어진 복합체 용액을 균질화기로 고르게 혼합하는 공정을 추가로 포함할 수 있으며, 이때 균질화기로는 초음파 균질화기 또는 회전식 균질화기를 사용하는 것이 적절하다.In addition, in
단계 3에서는 단계 2에서 생성된 복합체 용액을 분무 열분해하는 공정이 수 행되는데, 예를 들면 도 1에 나타낸 바와 같이, 복합체 용액을 촉매액 주입구(6)로, 질소가스를 질소가스 주입구(7)로 주입하여 스프레이 노즐(8)을 통해 전기히터(1)를 장착한 고온의 반응챔버(2) 내로 촉매용액을 분사시키게 되며, 분사로 인해 미세화된 촉매 용액들이 반응챔버를 통과하는 동안 소결되어 담체에 금속이 담지된 형태의 촉매 입자가 생성물(4)로서 수거되며 질소가스는 필터(3)를 통해 가스배기구(5)로 배출되게 된다. 이러한 분무 열분해 공정 중에는 분사된 복합체 용액의 용매가 기화되고 전이금속 전구체의 금속과 유기물의 결합이 끊어지면서 담체 표면에서 금속의 결정화가 이루어져 담체와 촉매금속이 안정된 결합을 형성하게 된다. 이때, 분무 열분해 공정은 120 내지 1200℃, 바람직하게는 300 내지 700℃에서 수행될 수 있으며, 1200℃ 초과인 경우에는 금속의 기화가 발생하여 결과물의 조성이 불균일해질 수 있다. 단계 3에서 얻어진 안정된 상의 촉매금속은 표면 금속 중 80% 이상이 열분해된 전이금속으로 이루어진다.In step 3, a process of spray pyrolysis of the complex solution produced in
본 발명의 제조방법에서, 단계 2와 단계 3의 공정은 각각 분리되어 수행될 수 있으나, 도 2에 나타낸 바와 같이 연속적으로도 수행될 수 있다. 구체적으로, 담체 분말 또는 담체 분말의 슬러리(9)와 전이금속 전구체 용액(10)을 유량조절기(11)가 장착되어있는 노즐을 따라 균질화기(12) 내로 주입하여 단계 2의 균질화 공정을 수행한 후, 바로 상기에서 설명한 단계 3의 분무 열분해 공정을 도 1에 나타낸 바와 같이 수행할 수 있다.In the manufacturing method of the present invention, the process of
이러한 본 발명의 제조방법에 의하면, 도 3 및 도 4에서 볼 수 있는 바와 같이, 담체 표면에 고착된 상태로 평균입경 100 ㎚ 이하의 금속촉매 입자를 대량으로 생산할 수 있으므로, 탄소나노튜브의 대량생산 등에 유용하게 활용될 수 있다.According to the manufacturing method of the present invention, as can be seen in Figures 3 and 4, it is possible to produce a large amount of metal catalyst particles having an average particle diameter of 100 nm or less in a fixed state on the surface of the carrier, mass production of carbon nanotubes This can be usefully used.
이하, 본 발명을 실시예에 의해 상세히 설명한다.Hereinafter, the present invention will be described in detail by way of examples.
단, 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기 실시예에 한정되는 것은 아니다.However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited to the following examples.
실시예 1 Example 1
에탄올 10 L에 MgO 500 g을 첨가한 후 초음파 균질화기로 분산시켜 평균입경 14 ㎛의 판상입자를 갖는 MgO 분산용액을 얻었다. Fe(NO3)3·9H2O 859 g을 에탄올 5 L에 녹인 후, 여기에 86% 몰리브덴(Mo)산 분말 10.83 g을 물 700 ml에 녹인 것을 첨가하여 1 시간 동안 교반하였다. 여기에 상기에서 얻어진 MgO 분산용액을 첨가한 후 초음파 균질화기로 1 시간 동안 분산시켰으며, 얻어진 분산액을 도 1에 나타낸 바와 같은 분무 열분해기의 노즐에 주입한 후, 500℃ 가열 조건하에 스프레이 분사시켜 본 발명에 따른 촉매금속을 제조하였다. 이때, 노즐의 구멍사이즈는 500 ㎛이고, 가스는 질소가스를 사용하여 20 L 용량으로 균일 분사시켰다. 제조된 촉매금속은 주사전자현미경 및 투과전자현미경을 사용하여 관찰하였다. 500 g of MgO was added to 10 L of ethanol and dispersed by an ultrasonic homogenizer to obtain a MgO dispersion solution having platelets having an average particle diameter of 14 μm. After dissolving 859 g of Fe (NO 3 ) 3 .9H 2 O in 5 L of ethanol, 10.83 g of 86% molybdenum (Mo) acid powder was dissolved in 700 ml of water, followed by stirring for 1 hour. The MgO dispersion solution obtained above was added thereto, and then dispersed by an ultrasonic homogenizer for 1 hour. The obtained dispersion solution was injected into the nozzle of the spray pyrolysis machine as shown in FIG. A catalyst metal according to the invention was prepared. At this time, the hole size of the nozzle was 500 µm, and the gas was uniformly sprayed at a capacity of 20 L using nitrogen gas. The prepared catalyst metal was observed using a scanning electron microscope and a transmission electron microscope.
그 결과, 입자사이즈 분석기를 통한 크기 측정은 불가능하였으나, 도 3 및 도 4에 나타낸 바와 같이, 촉매 담체 표면에 고착된 20 내지 50 ㎚ 범위의 입경을 갖는 금속촉매 입자들을 관찰할 수 있었다.As a result, size measurement through a particle size analyzer was not possible, but as shown in FIGS. 3 and 4, metal catalyst particles having a particle size in the range of 20 to 50 nm fixed to the surface of the catalyst carrier were observed.
본 발명에 따른 탄소나노튜브 합성용 촉매금속의 제조방법은 기존 분무열분해 촉매금속 제조공정에서 얻을 수 없었던 100 nm 이하의 미세화된 촉매금속을 대량으로 생산할 수 있으므로, 탄소나노튜브의 대량생산 등에 유용하게 활용될 수 있다.The method for preparing a catalyst metal for synthesizing carbon nanotubes according to the present invention can produce a large amount of micronized catalyst metal of 100 nm or less, which could not be obtained in the conventional spray pyrolysis catalyst metal manufacturing process, and thus is useful for mass production of carbon nanotubes. Can be utilized.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100892753B1 (en) * | 2007-10-10 | 2009-04-15 | 세메스 주식회사 | Apparatus and method for preparing catalyst for systhesis of carbon-nano-tube |
| KR100913369B1 (en) * | 2007-12-24 | 2009-08-20 | 엠파워(주) | Process for Preparing Catalyst for Synthesis of Carbon Nanotubes using Atomizing Pyrolysis Method |
| KR100956421B1 (en) * | 2007-12-24 | 2010-05-06 | 엠파워(주) | Process for Preparing Catalyst for Synthesis of Carbon Nanotubes using Atomizing Pyrolysis Method |
| KR101357628B1 (en) * | 2008-12-10 | 2014-02-06 | 제일모직주식회사 | Metal Nano Catalyst, Method for Preparing thereof and Carbon Nanotube Synthesized Using the Same |
| WO2014046471A1 (en) * | 2012-09-18 | 2014-03-27 | Hanwha Chemical Corporation. | Method for preparing metal catalyst for preparing carbon nanotubes and method for preparing carbon nanotubes using the same |
| KR101401368B1 (en) * | 2012-09-28 | 2014-05-30 | 한국기계연구원 | Fabrication method of catalyst-carrier composite powder |
| US9006132B2 (en) | 2010-08-10 | 2015-04-14 | Korea Kumho Petrochemical Co., Ltd | Process for preparing catalyst composition for the synthesis of carbon nanotube with high yields using the spray pyrolysis method |
| KR20200141772A (en) | 2019-06-11 | 2020-12-21 | 전남대학교산학협력단 | Manufacturing method of catalyst for synthesis of carbon nanotube bundle and manufacturing method of carbon nanotube bundle using the same |
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2006
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| KR100892753B1 (en) * | 2007-10-10 | 2009-04-15 | 세메스 주식회사 | Apparatus and method for preparing catalyst for systhesis of carbon-nano-tube |
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| KR100956421B1 (en) * | 2007-12-24 | 2010-05-06 | 엠파워(주) | Process for Preparing Catalyst for Synthesis of Carbon Nanotubes using Atomizing Pyrolysis Method |
| KR101357628B1 (en) * | 2008-12-10 | 2014-02-06 | 제일모직주식회사 | Metal Nano Catalyst, Method for Preparing thereof and Carbon Nanotube Synthesized Using the Same |
| US9006132B2 (en) | 2010-08-10 | 2015-04-14 | Korea Kumho Petrochemical Co., Ltd | Process for preparing catalyst composition for the synthesis of carbon nanotube with high yields using the spray pyrolysis method |
| WO2014046471A1 (en) * | 2012-09-18 | 2014-03-27 | Hanwha Chemical Corporation. | Method for preparing metal catalyst for preparing carbon nanotubes and method for preparing carbon nanotubes using the same |
| KR101446116B1 (en) * | 2012-09-18 | 2014-10-06 | 한화케미칼 주식회사 | Metal catalyst for producing carbon nanotubes and method for preparing carbon nanotubes using thereof |
| KR101401368B1 (en) * | 2012-09-28 | 2014-05-30 | 한국기계연구원 | Fabrication method of catalyst-carrier composite powder |
| KR20200141772A (en) | 2019-06-11 | 2020-12-21 | 전남대학교산학협력단 | Manufacturing method of catalyst for synthesis of carbon nanotube bundle and manufacturing method of carbon nanotube bundle using the same |
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