JP2020508959A - 連続式工程を利用した多重壁カーボンナノチューブの製造方法 - Google Patents
連続式工程を利用した多重壁カーボンナノチューブの製造方法 Download PDFInfo
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- walled carbon
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- 239000002048 multi walled nanotube Substances 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 238000010924 continuous production Methods 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims abstract description 101
- 239000000843 powder Substances 0.000 claims abstract description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 44
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 44
- 239000002243 precursor Substances 0.000 claims abstract description 44
- 239000007789 gas Substances 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 238000005507 spraying Methods 0.000 claims abstract description 17
- 239000012159 carrier gas Substances 0.000 claims abstract description 14
- 150000002739 metals Chemical class 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 239000012535 impurity Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- 238000001069 Raman spectroscopy Methods 0.000 claims description 3
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 3
- 150000004703 alkoxides Chemical class 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 3
- 230000003595 spectral effect Effects 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 3
- 239000002071 nanotube Substances 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 28
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000005229 chemical vapour deposition Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005118 spray pyrolysis Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910002445 Co(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003570 air Substances 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
- 239000012298 atmosphere Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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Abstract
Description
Fe(NO3)3・9H2O、Co(NO3)3・6H2O、(NH4)6Mo7O24・4H2O、NH4VO3、(NH4)10H2(W2O7)6・9H2O、Al(NO3)3・9H2O、Mg(NO3)2・6H2OおよびZrO(NO3)2・2H2Oのうち下記表1の触媒組成に必要なそれぞれの前駆体を脱イオン水に溶解させて、前駆体溶液を製造した。前記前駆体溶液を時間当たり3Lずつ空気とともに反応器の内部に噴霧して熱分解することによって、触媒粉末を収得した。この際、熱分解条件は、空気の圧力は、3気圧、反応器の内部温度は、750℃であり、120分間連続的に運転した。
前記触媒粉末の見かけ密度は、マスシリンダーに触媒粉末を充填して重さを測定した後、測定された重さをマスシリンダーの体積で割って算出し、これと同じ方法でカーボンナノチューブの見かけ密度を測定した。また、カーボンナノチューブの合成収率は、「合成されたカーボンナノチューブの重さ(g)]/[投入された触媒粉末の重さ(g)]*100」の式によって計算し、エチレンの転換率は、「{(多重壁カーボンナノチューブの重量(g))−(触媒粉末の重量(g))}/{(炭素系ガス供給量(L))*(炭素系ガス1モルのうち炭素の重量(g/mol))/(22.4(L/mol))}*100」の式によって計算した。測定結果は、下記表2の通りである。
Claims (17)
- (a)金属前駆体を溶媒中に溶解させて、前駆体溶液を製造する段階;
(b)前記前駆体溶液を反応器の内部に噴霧しながら、熱分解させて、触媒粉末を形成する段階;および
(c)前記触媒粉末を600〜900℃に加熱した流動層反応器の内部に投入し、炭素系ガスと運搬ガスを噴射して、前記触媒粉末から多重壁カーボンナノチューブを合成する段階;を含み、
前記段階(a)〜(c)が連続式で行われ、
前記触媒粉末は、下記式1による金属成分を含む多重壁カーボンナノチューブの製造方法:
上記式中、
Maは、Fe、Ni、Co、Mn、Cr、Mo、V、W、SnおよびCuの中から選ばれた2種以上の金属であり、
Mbは、Mg、Al、SiおよびZrの中から選ばれた1種以上の金属であり、
xおよびyは、それぞれMaおよびMbのモル分率を示し、
x+y=10、2.0≦x≦7.5、2.5≦y≦8.0である。 - 前記触媒粉末は、厚さが0.5〜10μmである中空構造を有する、請求項1に記載の多重壁カーボンナノチューブの製造方法。
- 前記触媒粉末の見かけ密度が0.05〜0.70g/mLである、請求項1に記載の多重壁カーボンナノチューブの製造方法。
- 前記中空構造の中空比率が50体積%以上である、請求項2に記載の多重壁カーボンナノチューブの製造方法。
- 下記式2による転換率が80%以上である、請求項1に記載の多重壁カーボンナノチューブの製造方法:
- 前記炭素系ガスが、炭素数1〜4の飽和または不飽和炭化水素、一酸化炭素、ベンゼン、およびこれらのうち2以上の混合物よりなる群から選ばれた一つである、請求項1に記載の多重壁カーボンナノチューブの製造方法。
- 前記運搬ガスが、ヘリウム、窒素、アルゴン、およびこれらのうち2以上の混合物よりなる群から選ばれた一つである、請求項1に記載の多重壁カーボンナノチューブの製造方法。
- 前記金属前駆体が、金属の硝酸塩、硫酸塩、アルコキシド、クロライド、アセテート、カーボネート、およびこれらのうち2以上の混合物よりなる群から選ばれた一つである、請求項1に記載の多重壁カーボンナノチューブの製造方法。
- 前記段階(b)が、
(i)2〜5気圧の空気を運搬ガスとして供給し、外部空気を流入させて、前駆体溶液を反応器の内部に噴霧する段階;および
(ii)噴霧された前記前駆体溶液を600〜1,200℃で熱分解して、触媒粉末を形成する段階;
を含む、請求項1に記載の多重壁カーボンナノチューブの製造方法。 - 前記段階(c)が、
(i)流動層反応器を600〜900℃に加熱する段階;
(ii)反応器の上部で触媒粉末を供給し、反応器内で流動化させる段階;
(iii)炭素系ガスと運搬ガスを反応器の下部で回転翼を通じて供給する段階;および
(iv)前記回転翼による上昇気流により流動化した前記触媒粉末上に炭素を熱気相蒸着させる段階;
を含む、請求項1に記載の多重壁カーボンナノチューブの製造方法。 - 前記段階(c)以後に、
(d)前記多重壁カーボンナノチューブを前記流動層反応器から回収する段階;をさらに含む、請求項1に記載の多重壁カーボンナノチューブの製造方法。 - 前記(d)段階が、
(i)前記多重壁カーボンナノチューブを、窒素ガスを利用してサイクロンに移送する段階;および
(ii)前記サイクロンで前記多重壁カーボンナノチューブのうち不純物を除去して、多重壁カーボンナノチューブを選別する段階;
を含む、請求項11に記載の多重壁カーボンナノチューブの製造方法。 - 前記多重壁カーボンナノチューブが凝集して束型カーボンナノチューブとして存在する、請求項1に記載の多重壁カーボンナノチューブの製造方法。
- 前記束型カーボンナノチューブの平均束直径(bundle diameter)が0.5〜20μmであり、平均束長さ(bundle length)が10〜200μmである、請求項13に記載の多重壁カーボンナノチューブの製造方法。
- 前記多重壁カーボンナノチューブのラマン分光強度比IG/IDが0.7〜1.5である、請求項1に記載の多重壁カーボンナノチューブの製造方法。
- 前記多重壁カーボンナノチューブの平均直径が5〜50nmである、請求項1に記載の多重壁カーボンナノチューブの製造方法。
- 前記多重壁カーボンナノチューブの見かけ密度が0.01〜0.07g/mLである、請求項1に記載の多重壁カーボンナノチューブの製造方法。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080274277A1 (en) * | 2006-03-20 | 2008-11-06 | Alimorad Rashidi | Continuous process for producing carbon nanotubes |
JP2009161426A (ja) * | 2007-12-31 | 2009-07-23 | Semes Co Ltd | 流動層炭素ナノチューブの生成装置並びにそれを使用した炭素ナノチューブの生成設備及び方法 |
JP2009528238A (ja) * | 2005-12-19 | 2009-08-06 | ナンテロ,インク. | カーボンナノチューブの生成 |
US20120040186A1 (en) * | 2010-08-10 | 2012-02-16 | Korea Kumho Petrochemical Co., Ltd. | Process For Preparing Catalyst Composition For The Synthesis Of Carbon Nanotube With High Yields Using The Spray Pyrolysis Method |
KR101349674B1 (ko) * | 2007-08-07 | 2014-01-09 | 금호석유화학 주식회사 | 탄소나노튜브 합성 방법 및 장치 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1797950A1 (en) | 2005-12-14 | 2007-06-20 | Nanocyl S.A. | Catalyst for a multi-walled carbon nanotube production process |
KR100732623B1 (ko) * | 2006-01-17 | 2007-06-27 | (주)씨엔티 | 탄소나노튜브 대량합성장치 |
CN101049927B (zh) * | 2007-04-18 | 2010-11-10 | 清华大学 | 连续化生产碳纳米管的方法及装置 |
KR100969860B1 (ko) * | 2008-12-29 | 2010-07-13 | 금호석유화학 주식회사 | 탄소나노튜브 제조용 촉매조성물 |
KR100976174B1 (ko) * | 2009-02-13 | 2010-08-16 | 금호석유화학 주식회사 | 얇은 다중벽 탄소나노튜브 제조용 촉매조성물 및 이의 제조방법 |
KR100969861B1 (ko) * | 2009-03-13 | 2010-07-13 | 금호석유화학 주식회사 | 비정질 실리콘 입자 함유 복합담지체를 포함하는 탄소나노튜브 제조용 촉매 및 이를 이용한 탄소나노튜브 대량 합성 방법 |
KR101329384B1 (ko) * | 2011-04-05 | 2013-11-14 | 주식회사 엘지화학 | 가스 분리 유닛을 갖는 카본나노튜브의 연속 제조장치 및 이를 이용한 연속 제조방법 |
KR101350690B1 (ko) | 2012-02-13 | 2014-01-14 | 금호석유화학 주식회사 | 초저밀도 특성을 지닌 번들 구조의 고전도성 탄소나노튜브 및 이의 제조방법 |
KR101303061B1 (ko) * | 2012-09-25 | 2013-09-03 | 금호석유화학 주식회사 | 다중벽 탄소나노튜브 제조용 촉매조성물 |
KR101771290B1 (ko) | 2014-06-13 | 2017-08-24 | 주식회사 엘지화학 | 탄소 나노구조물의 제조장치 및 제조방법 |
CN106215964B (zh) * | 2016-06-29 | 2019-01-18 | 北京化工大学 | 一种析氢催化剂及其制备方法 |
-
2018
- 2018-02-28 KR KR1020180024472A patent/KR102053726B1/ko active IP Right Grant
- 2018-03-02 US US16/490,772 patent/US11117803B2/en active Active
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009528238A (ja) * | 2005-12-19 | 2009-08-06 | ナンテロ,インク. | カーボンナノチューブの生成 |
US20080274277A1 (en) * | 2006-03-20 | 2008-11-06 | Alimorad Rashidi | Continuous process for producing carbon nanotubes |
KR101349674B1 (ko) * | 2007-08-07 | 2014-01-09 | 금호석유화학 주식회사 | 탄소나노튜브 합성 방법 및 장치 |
JP2009161426A (ja) * | 2007-12-31 | 2009-07-23 | Semes Co Ltd | 流動層炭素ナノチューブの生成装置並びにそれを使用した炭素ナノチューブの生成設備及び方法 |
US20120040186A1 (en) * | 2010-08-10 | 2012-02-16 | Korea Kumho Petrochemical Co., Ltd. | Process For Preparing Catalyst Composition For The Synthesis Of Carbon Nanotube With High Yields Using The Spray Pyrolysis Method |
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