JP6083624B2 - 炭素ナノチューブ集合体のバルク密度の調節方法 - Google Patents
炭素ナノチューブ集合体のバルク密度の調節方法 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 165
- 239000002041 carbon nanotube Substances 0.000 title claims description 135
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims description 135
- 238000000034 method Methods 0.000 title claims description 40
- 239000003054 catalyst Substances 0.000 claims description 119
- 238000010304 firing Methods 0.000 claims description 57
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- 230000035484 reaction time Effects 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 150000007524 organic acids Chemical class 0.000 claims description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- 230000007423 decrease Effects 0.000 claims description 5
- 239000002131 composite material Substances 0.000 description 20
- 238000005087 graphitization Methods 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 239000007789 gas Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000001354 calcination Methods 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- -1 biotechnology Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
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- 239000002245 particle Substances 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000002595 Solanum tuberosum Nutrition 0.000 description 2
- 244000061456 Solanum tuberosum Species 0.000 description 2
- 238000001241 arc-discharge method Methods 0.000 description 2
- 239000002717 carbon nanostructure Substances 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000002079 double walled nanotube Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
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- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- 238000003756 stirring 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
- 238000004438 BET method Methods 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910002546 FeCo Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000002110 nanocone Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
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- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- 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
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/31—Density
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
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- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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- 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
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8877—Vanadium, tantalum, niobium or polonium
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- C01B2202/00—Structure or properties of carbon nanotubes
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- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/22—Electronic properties
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Description
[数式1]
y=a1x1+b1
[数式3]
0.1x3+1≦LogR≦0.1x3+4
[数式1]
y=a1x1+b1
炭素ナノチューブ集合体の収率(倍)=(反応後の総重量g−使用した担持触媒の重量g)/使用した担持触媒の重量g
扁平率=炭素ナノチューブの中心を貫通する最小直径/炭素ナノチューブの中心を貫通する最大直径
[数式3]
0.1x3+1≦LogR≦0.1x3+4
0.1x3+2≦LogR≦0.1x3+3
A.グラファイト化金属触媒の前駆体水溶液の製造
グラファイト化触媒としてFe金属触媒を用意した。Feの前駆体物質としてFe(NO3)2・6H2O 2,424gを水2,000gに投入した。製造された金属水溶液は、沈殿が見えない綺麗な溶液状態で観察された。
アルミニウム系支持体前駆体として水酸化アルミニウム(Aluminum−tri−hydroxide,Al(OH)3)を300〜500℃で4時間の間第1焼成して得られた支持体2,000gをフラスコBに用意した。XRD分析によれば、焼成後の支持体は、AlO(OH)を40重量%以上含むものと表された。
300〜500℃で4時間の間第1焼成して得られた支持体2,000gをモル基準100に換算すれば、Feが30モルになるように、フラスコBに前記フラスコAの溶液4,424gを添加した。混合物の重量を測定した後、グラファイト化金属触媒の前駆体を十分にATH400に担持させるために、60℃の恒温槽で5分間撹拌して熟成させた。それを前記温度に維持しながら80rpmで回転させ、真空乾燥させた後、乾燥後の重量を測定して水分除去量を測定した(約14.1%)。乾燥した触媒を550〜700℃で4時間の間第2焼成して担持触媒を製造した。
前記で製造された炭素ナノチューブ合成用担持触媒を用いて、実験室規模の固定層反応装置で炭素ナノチューブの合成を行った。
触媒焼成温度によるバルク密度の変化を観察した。Feの代わりにCo/V(10:1モル比)を使用し、第1焼成温度を400℃にし、第2焼成温度を600〜700℃に変化させ、クエン酸を添加したこと(クエン酸1モルに対してCo23モル)を除いては、実施例1と同様な方法により触媒を製造した後、これを用いて炭素ナノチューブ集合体を合成した。反応時間を1時間及び2時間にした場合、炭素ナノチューブ集合体の収率及びバルク密度は以下のとおりである。
第1焼成温度を400℃にし、第2焼成温度を675℃にしたことを除いては、実施例2と同様な方法により触媒を製造した後、これを用いて炭素ナノチューブ集合体を合成した。反応時間を1時間及び2時間にした場合、コバルト含量の変化による炭素ナノチューブ集合体の収率及びバルク密度は以下のとおりである。
クエン酸1モルに対してCo含量を5.8モルにしたことを除いては、実施例3と同様な方法により触媒を製造した後、これを用いて炭素ナノチューブ集合体を合成した。反応時間を1時間及び2時間にした場合、コバルト含量の変化による炭素ナノチューブ集合体の収率及びバルク密度は以下のとおりである。
[数式1]
y=a1x1+b1
有機酸の添加によるバルク密度を観察した。クエン酸1モルに対してコバルト含量を変化させながら、炭素ナノチューブ集合体の収率及びバルク密度を観察した。その結果は下記表5に示した。
実施例2と下記表6に示すように触媒を使用し、窒素:エチレン:水素の割合を5.5:1:1にして、実験室規模の流動層反応器上で2時間反応させて炭素ナノチューブ集合体を製造した。具体的には、炭素ナノチューブ合成用触媒を、直径58mmの内径と長さ1200mmの石英管反応器で、窒素雰囲気で675℃まで昇温した後に維持させ、窒素、水素及びエチレンガスの体積混合比を5.5:1:1で分当たり総4000ml流しながら2時間の間合成して、所定量の炭素ナノチューブ集合体を合成した。
[数式3]
0.1x3+1≦LogR≦0.1x3+4
Claims (11)
- 水酸化アルミニウムを100〜500℃の第1焼成温度で焼成して支持体を形成し、
前記支持体に触媒金属前駆体を担持させた後、100〜800℃の第2焼成温度で焼成して得られた担持触媒を炭素含有化合物と加熱下で接触反応させて炭素ナノチューブ集合体を製造する方法において、
前記担持触媒を製造する際、触媒金属に対して有機酸を5:1〜30:1のモル比で添加し、有機酸の添加量を調節して、炭素ナノチューブ集合体のバルク密度を調節することを含み、
前記第1焼成温度、第2焼成温度、触媒の担持量、または反応時間を調節して、10kg/m3以上のバルク密度を有する炭素ナノチューブ集合体を製造する方法。 - 前記炭素ナノチューブ集合体の前記バルク密度が、100kg/m3以下である請求項1に記載の方法。
- 前記炭素ナノチューブ集合体の少なくとも一部が、バンドル型である請求項1または請求項2に記載の方法。
- 前記第2焼成温度は、前記第1焼成温度よりも200〜400℃高い請求項1から請求項3のいずれか一項に記載の方法。
- 前記第1焼成温度は300〜500℃であり、前記第2焼成温度は550〜800℃である請求項1から請求項4のいずれか一項に記載の方法。
- 前記触媒金属は、Fe、Coまたはこれらの組み合わせを含む請求項1から請求項5のいずれか一項に記載の方法。
- 前記第2焼成温度が675℃よりも低い区間では、第2焼成温度が高くなるほど、炭素ナノチューブ集合体のバルク密度が増加し、前記第2焼成温度が675℃よりも高い区間では、第2焼成温度が高くなるにつれて、炭素ナノチューブ集合体のバルク密度が減少する請求項1から請求項6のいずれか一項に記載の方法。
- 前記触媒金属の含量は、触媒の総重量を基準として5〜30重量%である請求項1から請求項7のいずれか一項に記載の方法。
- 前記触媒金属の含量(x1)と、炭素ナノチューブ集合体のバルク密度(y)とが下記数式1の関係を満たしている請求項1から請求項8のいずれか一項に記載の方法:
[数式1]
y=a1x1+b1
前記数式1中、yはバルク密度(kg/m3)、x1は触媒の総重量を基準とした触媒金属の含量であって、10〜30wt%、a1は反応時間によって決定される4〜7の定数、b1は反応時間によって決定される−15〜−40の定数である。 - 前記炭素含有化合物との反応時間(hr)に比例して、炭素ナノチューブ集合体のバルク密度が1.2〜1.5倍増加する請求項1から請求項9のいずれか一項に記載の方法。
- 前記炭素含有化合物との反応は、流動層反応器で行われる請求項1から請求項10のいずれか一項に記載の方法。
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |